Compositions comprising a superhydrophilic amphiphilic copolymer and a micellar thickener

ABSTRACT

Provided are healthcare compositions comprising a superhydrophilic amphiphilic copolymer, a micellar thickener, and a cosmetically-acceptable or pharmaceutically-acceptable carrier. Also, provided are methods of cleansing or treating a mammal by applying healthcare compositions of the present inventions to the mammalian body.

FIELD OF INVENTION

The present invention relates to compositions comprisingsuperhydrophilic amphiphilic copolymers and, in particular, compositionscomprising superhydrophilic amphiphilic copolymers that are useful inhealthcare applications and have relatively low irritation and highflash-foaming associated therewith.

DESCRIPTION OF THE RELATED ART

Synthetic detergents, such as cationic, anionic, amphoteric, andnon-ionic surfactants, are used widely in a variety of detergent andcleansing compositions to impart cleansing properties thereto. Inaddition, in certain compositions (e.g. personal care compositions suchas shampoos, washes, etc.), it may be desirable to use combinations andlevels of surfactants sufficient to achieve relatively high foam volumeand/or foam stability.

However, as is recognized in the art, synthetic detergents tend to beirritating to the skin and eyes. Thus, as levels of such detergents areincreased in attempts to increase cleansing and foaming propertiesassociated with certain compositions, the irritation associated withsuch compositions also tends to increase, making them undesirable foruse on or near the skin and/or eyes.

Certain attempts to produce milder cleansing compositions have includedcombining relatively low amounts of anionic surfactants (which tend tobe relatively high-foaming but also relatively highly irritating), withrelatively lower irritating surfactants such as nonionic and/oramphoteric surfactants. See, e.g. U.S. Pat. No. 4,726,915. Anotherapproach to producing mild cleansing compositions is to associate theanionic surfactants with amphoteric or cationic compounds in order toyield surfactant complexes. See, e.g., U.S. Pat. Nos. 4,443,362;4,726,915; 4,186,113; and 4,110,263. Disadvantageously, mild cleansingcompositions produced via both of such methods tend to suffer fromrelatively poor foaming and cleansing performance. Yet another approachdescribed in, Librizzi et al., (in United States Published PatentApplication US20050075256 A1) discusses the use of a compositionincluding both a hydrophobically modified polymer and a surfactant toprovide low irritation cleansing composition.

Still another approach to producing mild cleansing compositions is touse polymerized surfactants having a relatively lowdegree-of-polymerization and at least about 10 mol % amphiphilic repeatunits. See U.S. Pat. No. 7,417,020.

However, while improvements have made been in mildness, the inventorshave recognized that additional improvements in mildness are desirable,particularly improvements in both mildness and the ability ofcompositions to provide exceptional so-called “flash foam,” i.e., theability to form a high volume of foam with relatively low amount ofenergy input.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph of the foam generation rate of a composition of thepresent invention and a comparative example.

SUMMARY OF THE INVENTION

The present invention provides compositions, including healthcare andnon-healthcare compositions, that overcome the disadvantages of theprior art and have relatively low irritation properties associatedtherewith. In particular, applicants have discovered that certainpolymeric materials may be used to great advantage to producecompositions having low irritation associated therewith and, in certainembodiments, combinations of additional beneficial aesthetic and otherproperties. In addition, applicants have discovered that in certainembodiments the polymeric materials of the present invention may becombined with micellar thickeners to produce compositions that exhibitsignificant and unexpected amounts of flash foaming.

According to one aspect, the present invention provides compositionscomprising a superhydrophilic amphiphilic copolymer and a carrier. Suchcompositions may include healthcare and/or non-healthcare compositions.

According to another aspect, the present invention provides compositionscomprising a superhydrophilic amphiphilic copolymer, a micellarthickener, and a carrier.

DESCRIPTION OF PREFERRED EMBODIMENTS

All percentages listed in this specification are percentages by weight,unless otherwise specifically mentioned.

As used herein, the term “healthcare” refers to the fields of personalcare and medical care including, but not limited to, infant care, oralcare, sanitary protection, skin care, including the treatment of adultor infant skin to maintain the health of the skin, improve the health ofthe skin, and/or improve the appearance of the skin, wound care,including the treatment of a wound to assist in the closure or healingof a wound, and/or to reduce the pain or scarring associated with thewound, women's health, including the treatment of tissue in the internalor external vaginal area and/or breast, maintaining or improving thehealth of such tissue or skin, repairing such tissue or skin, reducingirritation of such tissue or skin, maintaining or improving theappearance of such tissue or skin, and improving or enhancing sexualfunction associated with such tissue or skin, and the like.

As used herein, the term “superhydrophilic amphiphilic copolymer,”(“SAC”) is defined as a copolymer that may be represented by thefollowing general structure:

wherein an “SRU” is a superhydrophilic repeat unit as defined herein, an“ARU” is an amphiphilic repeat unit as defined herein, an “HRU” is ahydrophilic repeat unit as defined herein, wherein s≧2, a>0, h≧0, andthe total number of repeat units, s+a+h is between 4 and about 1000. Theterm “between,” when used herein to specify a range such as “between 4and about 1000,” is inclusive of the endpoints, e.g. “4” and “about1000.” The total number of repeat units in the SAC is based on theweight-average molecular weight (M_(W)) of the SAC; thus the number ofrepeat units, as discussed herein are “weight average” as well. Further,all molecular weights described herein are in the units of Daltons (Da).As will be recognized by one of skill in the art, the pattern of repeatunits (SRUs, ARUs, HRUs) incorporated in SACs of the present inventionare generally random; however, they may also have alternating,statistical, or blocky incorporation patterns. In addition, SACarchitectures may be linear, star-shaped, branched, hyperbranched,dendritic, or the like.

Those of skill in the art will recognize that total number of repeatunits in a SAC (SRUs+ARUs+HRUs, i.e. s+a+h in the above formula) issynonymous with the term “degree of polymerization” (“DP”) of the SAC.

A “repeat unit” as defined herein and known the art is the smallest atomor group of atoms (with pendant atoms or groups, if any) comprising apart of the essential structure of a macromolecule, oligomer, block, orchain, the repetition of which constitutes a regular macromolecule, aregular oligomer molecule, a regular block, or a regular chain(definition from Glossary of Basic Terms in Polymer Science, A. D.Jenkins et al. Pure Appl. Chem. 1996 68, 2287-2311.) As will berecognized by those of skill in the art in light of the descriptionherein and knowledge of the art, the backbone of a polymer derived fromethylenically-unsaturated monomers comprises repeat units including oneor two, or in the case of alternating polymers four, carbon atoms thatwere unsaturated in the monomers prior to polymerization, and anypendant groups of such carbons. For example, polymerization of anethylenically-unsaturated monomer of the formula: (A)(Y)C═C(B)(Z) willgenerally result in a polymer comprising repeat units of the formula:

comprising the two previously unsaturated carbons of the monomer andtheir pendant groups (examples of which are described herein below, forexample in the descriptions of SRUs, ARUs, and HRUs.) However, if thependant groups of the two carbons are the same such that, for example inthe formula above, A-C—Y and B—C—Z are the same moiety, then each ofsuch one carbon units and its pendant groups (A-C—Y or B—C—Z, being thesame) are considered to be the repeat unit comprising only onepreviously unsaturated carbon from the monomer (e.g. the repeat unit ofa homopolyer derived from ethylene, H₂C═CH₂ is [—[CH₂]—] not[—[CH₂CH₂]—]. With regard only to alternating copolymers, which as knownin the art are defined as those polymers in which the repeat unitsderived from the two comonomers alternate consistently throughout thepolymer (as opposed to the random polymerization of co-monomers to forma polymer in which repeat units derived from the two monomers arerandomly linked throughout the polymer or the block copolymerization ofcomonomers to form non-alternating blocks of repeat units derived fromthe two monomers), the repeat unit is defined as the unit derived fromone of each of the co-monomers comprising four carbons that werepreviously ethylenically-unsaturated in the two comonomers prior topolymerization. That is, maleic anhydride and vinyl methyl ether areused in the art to form an alternating copolymer, poly(maleicanhydride-alt-vinyl methyl ether) having repeat units of the structure:

For saccharide-based polymers whose backbone is formed by linking sugarrings, the repeat unit generally comprises the sugar ring and pendantgroups (as shown herein below, for example in the descriptions of SRUs,ARUs, and HRUs.) Examples of such repeat units also include sugar ringrepeat units with pendant sugar rings, for example, Galactomannans arepolysaccharides comprised of a mannose (monosaccharide-based) backbone.Pending from some but not all of the mannose groups in the backbone (andarranged in either a random or block fashion) are pendant galactosegroups. As will be readily understood by one skilled in the art, thisstructure is best described as having, two repeat units, mannose andmannose-galactose.

For alternating saccharide-based polymers, then the repeat unit is thetwo sugar rings derived from the alternating sugar-based monomers andtheir pendant groups. For example, Hyaluronan is an alternatingsaccharide copolymer derived from two saccharides, D-glucuronic acid andD-N-acetylglucosamine that alternate to give a disaccharide repeatunits.

A “hydrophobic moiety” is hereby defined as a nonpolar moiety thatcontains at least one of the following: (a) a carbon-carbon chain of atleast four carbons in which none of the four carbons is a carbonylcarbon or has a hydrophilic moiety bonded directly to it; (b) two ormore alkyl siloxy groups (—[Si(R)₂—O]—); and/or (c) two or moreoxypropylene groups in sequence. A hydrophobic moiety may be, orinclude, linear, cyclic, aromatic, saturated or unsaturated groups. Incertain preferred embodiments, hydrophobic moieties comprise a carbonchain of at least six or more carbons, more preferably seven or morecarbons in which none of the carbons in such chain have a hydrophilicmoiety bonded directly thereto. Certain other preferred hydrophobicmoieties include moieties comprising a carbon chain of about eight ormore carbon atoms, more preferably about 10 or more carbon atoms inwhich none of the carbons in such chain have a hydrophilic moiety bondeddirectly thereto. Examples of hydrophobic functional moieties mayinclude esters, ketones, amides, carbonates, urethanes, carbamates, orxanthate functionalities, and the like, having incorporated therein orattached thereto a carbon chain of at least four carbons in which noneof the four carbons has a hydrophilic moiety bonded directly to it.Other examples of hydrophobic moieties include groups such aspoly(oxypropylene), poly(oxybutylene), poly(dimethylsiloxane),fluorinated hydrocarbon groups containing a carbon chain of at leastfour carbons in which none of the four carbons has a hydrophilic moietybonded directly to it, and the like.

As used herein, the term “hydrophilic moiety,” is any anionic, cationic,zwitterionic, or nonionic group that is polar. Nonlimiting examplesinclude anionics such as sulfate, sulfonate, carboxylicacid/carboxylate, phosphate, phosphonates, and the like; cationics suchas: amino, ammonium, including mono-, di-, and trialkylammonium species,pyridinium, imidazolinium, amidinium, poly(ethyleneiminium), and thelike; zwitterionics such as ammonioalkylsulfonate,ammonioalkylcarboxylate, amphoacetate, and the like; and nonionics suchas hydroxyl, sulfonyl, ethyleneoxy, amido, ureido, amine oxide, and thelike.

As used herein, the term “superhydrophilic repeat unit,” (“SRU”) isdefined as a repeat unit that comprises two or more hydrophilic moietiesand no hydrophobic moieties. For example, SRUs may be derived fromethylenically-unsaturated monomers having two or more hydrophilicmoieties and no hydrophobic moieties, including repeat units of thegeneral formulae:

wherein A, B, Y, and Z collectively include at least two hydrophilicmoieties and no hydrophobic moieties; or

wherein W and X collectively include at least two hydrophilic moieties.Illustrative examples of such SRUs include, but are not limited to,those derived from superhydrophilic monomers described herein and thelike, such as:

which is derived from glyceryl methacrylate; or others such as

which is derived from 4-Hydroxybutyl itaconate; and the like.

Other examples of SRUs include saccharide-based repeat units includingrepeat units derived from fructose, glucose, galactose, mannose,glucosamine, mannuronic acid, guluronic acid, and the like, such as:

wherein A, B, U, V, W, X, Y, and Z collectively include at least twohydrophilic moieties and no hydrophobic moieties, one example of whichincludes

which is a α(1→4)-D-glucose SRU; or

wherein A, B, U, V, and W collectively include at least two hydrophilicmoieties and no hydrophobic moieties, one example of which includes

a β(2→1)-D-fructose SRU; and the like. As will be recognized by those ofskill in the art, monosaccharide repeat units may be linked in variousfashions, that is, through various carbons on the sugar ring e.g. (1→4),(1→6), (2→1), etc. Any of such linkages, or combinations thereof, may besuitable for use herein in monosaccharide SRUs, ARUs, or HRUs.

Other examples of SRUs include repeat units derived from amino acids,including, for example, repeat units of the formula:

wherein R includes a hydrophilic repeat unit, examples of which include

an aspartic acid SRU, and the like.

As used herein, the term “amphiphilic repeat unit,” (“ARU”) is definedas a repeat unit that comprises at least one hydrophilic moiety and atleast one hydrophobic moiety. For example, ARUs may be derived fromethylenically-unsaturated monomers having at least one hydrophilicmoiety and at least one hydrophobic moiety, including repeat units ofthe general formulae

wherein A, B, Y, and Z collectively include at one hydrophilic moietyand at least one hydrophobic moiety; or

wherein W and X collectively include at one hydrophilic moiety and atleast one hydrophobic moiety; examples of which include

sodium 2-acrylamidododecylsulfonate amphiphilic repeat unit (ARU), andthe like.

Other examples of ARUs include saccharide-based repeat units includingrepeat units derived from including repeat units derived from fructose,glucose, galactose, mannose, glucosamine, mannuronic acid, guluronicacid, and the like, such as:

wherein A, B, U, V, W, X, Y, and Z collectively include at least onehydrophilic moiety and at least one hydrophobic moiety, or

wherein A, B, U, V, and W collectively include at least one hydrophilicmoiety and at least one hydrophobic moiety, examples of which include

1,2-epoxydodecane modified α(1→4)-D-glucose ARU, and the like.

Other examples of ARUs include repeat units derived from amino acids,including, for example, repeat units of the formula:

wherein R includes a hydrophobic group, examples of which include

a phenylalanine ARU; and the like.

As will be readily understood by those of skill in the art, the term“hydrophilic repeat unit,” (“HRU”) is defined as a repeat unit thatcomprises one and only one hydrophilic moiety and no hydrophobicmoieties. For example, HRUs may be derived fromethylenically-unsaturated monomers having one and only one hydrophilicmoiety and no hydrophobic moieties, including repeat units of thegeneral formulae

wherein A, B, Y, and Z collectively include one and only one hydrophilicmoiety and no hydrophobic moieties; or

wherein W and X collectively include one and only one hydrophilic moietyand no hydrophobic moieties, examples of which include

methacrylic acid hydrophilic repeat unit (HRU); and the like.

Other examples of HRUs include saccharide-based repeat units includingrepeat units derived from fructose, glucose, galactose, mannose,glucosamine, mannuronic acid, guluronic acid, and the like, such as:

wherein A, B, U, V, W, X, Y, and Z collectively include one and only onehydrophilic moiety and no hydrophobic moieties, or

wherein A, B, U, V, and W collectively include one and only onehydrophilic moiety and no hydrophobic moieties. One example ofsaccharide-based hydrophilic repeat unit includes methylcellulose HRU,(methyl-substituted poly[β(1→4)-D-glucose], DS=2.0)

Other examples of HRUs include repeat units derived from amino acids,including, for example, repeat units of the formula:

wherein R is neither a hydrophilic nor hydrophobic moiety, one exampleof which includes

alanine HRU; and the like. As will be recognized by one of skill in theart, in any of the formulae herein, examples of moieties that areneither hydrophilic nor hydrophobic include hydrogen, C₁-C₃ alkyl,C₁-C₃alkoxy, C₁-C₃ acetoxy, and the like.

As noted above, applicants have discovered unexpectedly that certainSACs are suitable for use in producing compositions having relativelylow irritation and relatively high amounts of foam associated therewith.In certain other embodiments, wherein such SACs are in combination withmicellar thickeners, the SACs are suitable for use in producingcompositions that further exhibit relatively high amounts of flashfoaming. According to certain preferred embodiments, applicants havediscovered that SACs having a DP between 4 and about 1000 repeat units,exhibit such significant and unexpected combination of low-irritationand high foaming properties and are suitable for use in embodiments withmicellar thickeners to exhibit high flash foaming. Examples of preferredSACs suitable for use in accord with such embodiments, include thosehaving a DP of between 4 and about 500, more preferably 4 and about 200,more preferably 4 and about 100, more preferably 4 and about 50 repeatunits. Other examples include those having a DP of between 5 and about500, more preferably 5 and about 200, more preferably 5 and about 100,more preferably 5 and about 50 repeat units. Other examples includethose having a DP of between 6 and about 200, more preferably 6 andabout 100, more preferably 6 and about 50 repeat units. Other examplesinclude those having a DP of between 7 and about 100, more preferably 7and about 50 repeat units.

According to certain embodiments, applicants have further discoveredthat certain SACs are capable of forming compositions having relativelylow “Dynamic Surface Tension Reduction Time” (that is, the time requiredto reduce surface tension of pure water from 72 mN/m to 55 mN/m,“t_(γ=55)”, associated with a particular composition, which value ismeasured conventionally via the prop Shape Analysis Test (“DSA Test”)described in further detail in the Examples below) and are preferred foruse in compositions having significant and unexpected combinations oflow-irritation and high foaming properties, and in certain embodimentshigh flash-foaming, as compared to comparable compositions. According tocertain preferred embodiments, the SACs of the present invention have at_(γ=55) of about 120 seconds (s) or less. In certain more preferredembodiments, the SACs of the present invention have a t_(γ=55) of about75 seconds or less, more preferably about 50 or less, more preferablyabout 45 or less.

Applicants have further discovered that while a variety of conventionalpolymers, including ones having higher DPs and/or more ARUs than SACs ofthe present invention, are designed specifically to increase theviscosity of a composition in small amounts, certain SACs of the presentinvention tend to have relatively small effect on the rheology of thecompositions to which they are added. Accordingly, in certainembodiments, higher amounts of the present SACs may be added to moresignificantly reduce irritation, create relatively fast and copiousfoam, without producing a composition that is too viscous for effectivepersonal use. In particular, suitable SACs include those having asolution viscosity (measured in accord with the “Solution ViscosityTest,” described herein below and shown in the Examples) of about 9centipoise (cP) or less. In certain more preferred embodiments, the SACsof the present invention have a solution viscosity of about 7 cps orless, more preferably about 4 cps or less, more preferably about 3 cpsor less.

According to certain preferred embodiments, SACs suitable for use in thepresent invention exhibit a mole percent (mol %) of amphiphilic repeatunits (amphiphilic mol %=(a/s+a+h)) of less than 10%. In certainpreferred embodiments, such SACs include those having a mol % of ARUs offrom about 0.1 to 9.9 mol %, more preferably from about 0.1 to about 9.4mol %, more preferably from about 0.1 to about 8.5 mol %, and morepreferably from about 0.1 to about 8.0 mol %. In certain preferredembodiments, the SACs include those having a mol % of ARUs of from about0.5 to about 9.4 mol %, more preferably from about 0.5 to about 8.5 mol%, and more preferably from about 0.5 to about 8.0 mol %. In certainpreferred embodiments, the SACs include those having a mol % of ARUs offrom about 1 to about 8.5 mol %, and more preferably from about 1 toabout 8.0 mol %.

The SACs of the present invention may be of any suitable molecularweight (provided the required DP is met). In certain preferredembodiments, the SAC has a weight average molecular weight from about1000 grams/mol to about 200,000 grams/mol. In a preferred embodiment,the SAC has a weight average molecular weight of from about 1000 toabout 100,000, more preferably from about 1,000 to about 75,000, morepreferably from about 1,000 to about 50,000, more preferably from about1,000 to about 25,000, and more preferably from about 1,000 to about10,000, and more preferably from about 3,000 to about 10,000.

SACs suitable for use in the present invention include polymers ofvarious chemical classifications and obtained via a variety of syntheticroutes. Examples include polymers having a backbone that substantiallycomprises a plurality of carbon-carbon bonds, preferably essentiallyconsists or consists only of carbon-carbon bonds and polymers having abackbone comprising a plurality of carbon-heteroatom bonds (as will berecognized by those of skill in the art, the backbone refers generallyto the portion of repeat units in a polymer that is covalently bonded toadjacent repeat units (vs. “pendant groups”).

Examples of synthetic routes for obtaining SACs of the present inventioninclude copolymerization of (i) one or more ethylenically unsaturatedamphiphilic comonomers with (ii) one or more ethylenically unsaturatedsuperhydrophilic comonomers, and optionally, (iii) one or moreethylenically unsaturated hydrophilic comonomers. Nonlimiting examplesof ethylenically unsaturated amphiphilic comonomers include those havingthe following structure:

-   -   where R₁=R₂=H, R₃=H or CH₃, and R₄ comprises Amphiphilic        (Amphil) group, or    -   where R₁=R₂=H, R₃ comprises a hydrophilic group (Hphil), and R₄        comprises hydrophobic group (Hphob), or    -   where R₁, R₃ are independently H or CH₃, R₂ comprises Hphil, and        R₄ comprises Hphob group, or    -   where R₁, R₄ are independently H or CH₃, R₃ comprises Hphil, and        R₄ comprises Hphob group, or    -   where R₂, R₃ are independently H or CH₃, R₁ comprises Hphil, and        R₄ comprises Hphob group        examples of which include:

Anionic:

-   -   ω-alkeneoates: e.g. sodium 11-undecenoate

-   -   where R₁=any linear or branched carbon chain containing more        than 5 carbon atoms and M=H⁺, NH₄ ⁺, or any Group IA alkali        metal cation.    -   (Meth)acrylamidoalkylcarboxylates and        (meth)acryloyloxyalkylcarboxylates: e.g. sodium        11-acrylamidoundecanoate, sodium 11-methacryloyloxyundecanoate

-   -   where R₂=H or CH₃, X=O or NH, R₃=any linear or branched carbon        chain containing more than 5 carbon atoms and M=H⁺, NH₄ ⁺, or        any Group IA alkali metal cation.    -   (Meth)acrylamidoalkylsulfonic acids: e.g.        2-acrylamidododecylsulfonic acid

-   -   where R₄=H or CH₃, X=O or NH, R₅=any linear or branched carbon        chain containing more than 5 carbon atoms and M=H⁺, NH₄ ⁺, or        any Group IA alkali metal cation.    -   Allylalkylsulfosuccinates: e.g. sodium        allyldodecylsulfosuccinate (TREM LF-40, Cognis)

-   -   where R₆=any linear or branched carbon chain containing more        than 5 carbon atoms and M=H⁺, NH₄ ⁺, or any Group IA alkali        metal cation.

Cationic:

-   -   Quaternized aminoalkyl(meth)acrylamides and        aminoalkyl(meth)acrylates: e.g.        (3-methacrylamidopropyl)dodecyldimethylammonium chloride,        (2-methacryloyloxyethyl)dodecyl dimethylammonium chloride

-   -   where R₇=H or CH₃, X=O or NH, R₈=any linear or branched carbon        chain containing 5 or less carbon atoms, R₉=H, CH₃, CH₂CH₃ or        CH₂CH₂OH, R₁₀=any linear or branched carbon chain containing        more than 5 carbon atoms and Z=any Group VII-A halide anion, OR        where R₇=H or CH₃, X=O or NH, R₈=any linear or branched carbon        chain containing more than 5 carbon atoms, R₉, R₁₀ are        independently H, CH₃, CH₂CH₃ or CH₂CH₂OH, and Z=any Group VII-A        halide anion    -   Quaternized vinylpyridines: e.g. (4-vinyl)dodecylpyridinium        bromide

-   -   where R₁₁=any linear or branched carbon chain containing more        than 5 carbon atoms and Z=any Group VII-A halide anion.    -   Alkyldiallylmethylammonium halides: e.g.        diallyldodecylmethylammonium chloride

-   -   where R₁₂=H, CH₃ or R₁₃, R₁₃=any linear or branched carbon chain        containing more than 5 carbon atoms and Z=any Group VII-A halide        anion.

Zwitterionic:

-   -   Ammonioalkanecarboxylates:        e.g. 2-[(11-(N-methylacrylamidyl)undecyl)dimethylammonio]acetate

-   -   where R₁₄=H or CH₃, X=O or N, R₁₅=H, CH₃, CH₂CH₃ or CH₂CH₂OH,        R₁₆=any linear or branched carbon chain more than 5 carbon        atoms, R₁₇=any linear or branched carbon chain containing 5 or        less carbon atoms, and R₁₈=H, CH₃, or nothing.    -   Ammonioalkanesulfonates: e.g.        3-[(11-methacryloyloxyundecyl)dimethylammonio]propanesulfonate

-   -   where R₁₉=H or CH₃, X=O or N, R₂₀=H, CH₃, CH₂CH₃ or CH₂CH₂OH,        R₂₁=any linear or branched carbon chain more than 5 carbon        atoms, R₂₂=any linear or branched carbon chain containing 5 or        less carbon atoms, and R₂₃=H, CH₃, or nothing.

Nonionic:

-   -   ω-methoxypoly(ethyleneoxy)alkyl-α-(meth)acrylates: e.g.        ω-methoxypoly(ethyleneoxy)undecyl-α-methacrylate

-   -   where R₂₄=H or CH₃, X=O, R₂₅=any linear or branched carbon chain        more than 5 carbon atoms, n is an integer from about 4 to about        800, and R₂₆=any linear or branched carbon chain containing 5 or        less carbon atoms    -   ω-alkoxypoly(ethyleneoxy)-α-(meth)acrylates and        ω-alkoxypoly(ethyleneoxy)-α-itaconates: e.g. steareth-20        methacrylate, ceteth-20 itaconate

-   -   where R₂₇=H, CH₃, or CH₂COOH, X=O, R₂₈=any linear or branched        carbon chain more than 5 carbon atoms, and n is an integer from        about 4 to about 800

Nonlimiting examples of ethylenically unsaturated superhydrophiliccomonomers include the following, and the like:

Nonionic:

-   -   glyceryl(meth)acrylate    -   sucrose mono(meth)acrylate, glucose mono(meth)acrylate        tris(hydroxymethyl)acrylamidomethane,        1-(2-(3-(allyloxy)-2-hydroxypropylamino)ethyl)imidazolidin-2-one        (Sipomer® WAM from Rhodia)

Anionic:

-   -   itaconic acid, hydrophilic derivatives thereof, and alkali metal        salts thereof    -   crotonic acid, hydrophilic derivatives thereof, and alkali metal        salts thereof    -   maleic acid, hydrophilic derivatives thereof, and alkali metal        salts thereof.

Cationic:

-   -   2-(meth)acryloyloxy-N-(2-hydroxyethyl)-N,N-dimethylethylammonium        chloride,        3-(meth)acrylamido-N-(2-hydroxyethyl)-N,N-dimethylpropylammonium        chloride,        3-(meth)acrylamido-N,N-bis(2-hydroxyethyl)-N-methylpropylammonium        chloride, N-(2-(bis(2-hydroxyethyl)amino)ethyl)(meth)acrylate,        N-(3-(bis(2-hydroxyethyl)amino)propyl)(meth)acrylamide,        N-(2-((meth)acryloyloxy)ethyl)-N,N,N′,N′,N′-pentamethylethane-1,2-diammonium        dichloride

Zwitterionic:

-   -   3-[(3-(meth)acrylamidopropyl)dimethylammonio]propanesulfonate,        3-(3-(meth)acrylamidopropyldimethylammonio)propionate,        3-(3-(meth)acrylamidopropyldimethylammonio)acetate,        2-(meth)acryloyloxyethylphosphorylcholine, and the like        Nonlimiting examples of optional ethylenically unsaturated        hydrophilic comonomers include the following, and the like:

Nonionic:

-   -   e.g. acrylamide, N,N-dimethylacrylamide, N-vinylformamide,        hydroxyethyl(meth)acrylate, (meth)acrylamidoethylethyleneurea,        ω-methoxypoly(ethyleneoxy)-α-(meth)acrylate, and the like

Anionic:

-   -   acrylic acid, β-carboxyethyl acrylate,        2-acrylamido-2-methylpropanesulfonic acid,        3-acrylamido-3-methylbutanoic acid, sodium        allylhydroxypropylsulfonate

Cationic:

-   -   N,N-dimethylaminoethyl methacrylate,        N,N-dimethylpropyl(meth)acrylamide,        (3-(meth)acrylamidopropyl)trimethylammonium chloride,        diallyldimethylammonium chloride

By way of non-limiting example, SACs made via copolymerization ofethylenically-unsaturated monomers include:

poly[tris(hydroxymethyl)acrylamidomethane-co-sodium2-acrylamidododecylsulfonate]

poly[glycerylmethacrylate-co-(2-methacryloyloxyethyl)dodecyldimethylammoniumchloride]; and the like.

Additional synthetic routes for achieving the SACs of the presentinvention include via post-polymerization modification of precursorpolymers comprising SRUs to render some repeat units amphiphilic.Nonlimiting examples include the reaction of superhydrophilic polymerscomprised of repeat units comprising multiple hydroxyl functionalities,for example, starch, hydroxyethylcellulose, dextran, inulin, pullulan,poly(glyceryl methacrylate),poly[tris(hydroxymethyl)acrylamidomethane)], or poly(sucrosemethacrylate), with reagents that will result in amphiphilic repeatunits. Examples of suitable reaction schemes include:

-   -   i) Esterification with alkenyl succinic anhydrides    -   ii) Etherification with 1,2-epoxyalkanes    -   iii) Etherification of with        3-chloro-2-hydroxypropylalkyldimethylammonium chlorides    -   iv) Esterification with monoalkyl phosphate esters

According to certain preferred embodiments, the SAC for use in thepresent invention is a polymer having multiple hydroxyl functionalitiesthat is then post-polymerization modified to convert some of the repeatunits to ARUs. In one particularly preferred embodiment, the polymer,e.g., a starch such as a starch dextrin polymer, that is esterified withan alkenyl succinic anhydride to convert some of the superhydrophilicanhydroglucose units to ARUs. The structure of one such suitableresulting SAC may be the C-6 sodium dextrin alkenylsuccinate,represented below:

For example, the SAC may be a sodium dextrin dodecenylsuccinate, ifR=C₁₂H₂₃. As will be recognized by one of skill in the art, such alkenylsuccinate esters of polysaccharides may be synthesized as described, forexample, in U.S. Pat. No. 2,661,349, incorporated herein by reference.Depending on the nature of the reaction conditions, moleculararchitecture, type of sugar repeat units, branch points and molecularweight, the modification of the sugar repeat units (AGU) may also occurat the C-2, C-3 or C-4 positions in addition to the C-6 position shownabove.

The superhydrophilic amphiphilic copolymers derived from the reaction ofthe starting polysaccharide with the hydrophobic reagent comprises apolysaccharide bound with the hydrophobic reagent. In certain preferredembodiments, the SAC is a starch-based polysaccharide modified with oneor more hydrophobic reagents. Examples of suitable starches includethose derived from such plants as corn, wheat, rice, tapioca, potato,sago, and the like. Such starches can be of a native variety or thosedeveloped by plant breeding or by gene manipulation. In an embodiment ofthe invention, the starches include either the waxy versions of suchstarches (containing less than 5% amylose), high amylose starches(containing more than 40% amylose), those with a modified chain length(such as those disclosed in U.S. Pat. No. 5,9545,883, which isincorporated by reference in its entirety herein), and/or combinationsthereof. In certain preferred embodiments, the starting starch is potatostarch or tapioca starch. In certain other preferred embodiments, thestarting starch is a waxy potato starch or waxy tapioca starch. Incertain embodiments, the starch-based polysaccharide is modified bydissolving such low molecular weight starch or “dextrin” in water andreacting such starch with a hydrophobic reagent. The starch is desirablyprocessed to lower its molecular weight by techniques known in the art,e.g., action of acid and heat, enzymatic, or thermal processing. The lowmolecular weight starch is dissolved in water, with optional heating, toform an aqueous solution and the pH of the aqueous solution is adjustedto about 2.0 by addition of an acid, such as a mineral acid (e.g.hydrochloric acid), to the solution. To minimize the removal of water atthe end of the reaction, it is preferred that the starch solution beprepared at the highest solids possible. In an exemplary embodiment, asuitable working range for aqueous solids of the low molecular weightstarch is from about 10% to about 80% starch based on the total weightof the solution. Preferably, the percent solids of the low molecularweight starch is from about 25% to about 75% based on total weight ofsolution. In another embodiment, the percent solids of the low molecularweight starch may be from about 35% to about 70% by weight of the totalsolution.

The viscosity of the aqueous solution of the polymeric surfactant isdesirably low to minimize the detrimental effect of a high solids levelof surfactant with pumping or flow of the solution. For this reason, inan embodiment of the invention, the Brookfield viscosity measured atroom temperature (about 23° C.) at 200 rpm using spindle #3 for thepolymeric surfactants of this invention may be less than about 1000 cpsat 10% aqueous solids based on the total weight of the solution. Inanother embodiment, the Brookfield viscosity measured at roomtemperature (about 23° C.) at 200 rpm using spindle #3 of the 10%aqueous solution may be less than about 25 cps. In yet anotherembodiment, the Brookfield viscosity measured at room temperature (about23° C.) at 200 rpm using spindle #3 of a 10% aqueous solution will beless than about 10 cps.

In a further step, the conversion of some of the superhydrophilicanhydroglucose units to ARUs is performed by reacting one or morehydrophobic reagents (e.g., alkenyl succinic anhydride) with the starchin the aqueous solution at a pH of about 8.5 at about 40° C. for about21 hours to form an aqueous solution of SAC. Additional process stepssuch as cooling the aqueous solution of SAC to about 23° C. andneutralizing the solution to a pH of about 7.0 may then be performed. Inan embodiment of the invention, the pH is adjusted by using a mineralacid, such as hydrochloric acid.

In certain preferred embodiments, the starch-based polysaccharide ismodified with alkenyl succinic anhydride. Surprisingly, it has beenfound that a substituted succinic anhydride containing a C12 or longerside chain provides improved foam volume and foam stability thansubstituted succinic anhydrides having less than a C12 side chain. Incertain preferred embodiments, the alkenyl succinic anhydrides isdodecenylsuccinic anhydride (DDSA). Exemplary treatment levels of theDDSA, on the dry basis of low molecular weight ranges from about 3 toabout 25%. In another embodiment, the treatment level may be from about5 to about 15% DDSA based on the dry weight of low molecular weightstarting starch.

In an embodiment of the invention, the superhydrophilic amphiphiliccopolymers derived from the reaction of the starting polysaccharide andDDSA, the bound DDSA on the starch-based polysaccharide may be of fromabout 3 about 15% based on the weight of dry starch. In anotherembodiment, the bound DDSA will be between 5 and 12% based on the dryweight of starch.

In an embodiment of the invention, the solution containing the lowmolecular weight polysaccharide may be then contacted with the DDSAusing sufficient agitation to keep the DDSA uniformly dispersedthroughout the solution. The reaction may then be run at temperaturesbetween 25° C. and 60° C. while the pH of the reaction is kept fromabout 7.0 and about 9.0 by the slow and controlled addition of asuitable base. Some examples of such suitable base materials include,but not limited to, sodium hydroxide, potassium hydroxide, sodium,carbonate, potassium carbonate and calcium oxide (lime) and the like.

The solution of superhydrophilic amphiphilic copolymers of thisinvention is desirably clear or slightly hazy in order to provideacceptable aesthetics in personal care applications. A solution of 10%of the polymer is preferably less than about 400 ntu (as described inthe experimental section below). In one embodiment, the clarity of a 10%aqueous solution of the polymeric surfactant is less than about 120 ntu.In another embodiment, the clarity is less than about 10 ntu.

In an exemplary embodiment of the invention, the hydrophobic reagent isa highly branched version of DDSA containing a 12 carbon side chain madefrom tetramerization of propene. It has been found that when thetetrapropene is then reacted with maleic anhydride in an ene-typereaction, it forms highly branched tetrapropenyl succinic anhydride(TPSA). Because this material is a slightly viscose oil and hasacceptable water solubility (e.g., at about 2-5% in water at 23° C.),this reagent is capable of reacting favorably with the low molecularweight polysaccharide. In an embodiment of this invention, therefore,the hydrophobic reagent used to modify the low molecular weight starchmay be TPSA.

In certain other preferred embodiments, the starch-based polysaccharideis modified with a long chain quaternary compound having at least onechain containing 3 or more carbon atoms. In another embodiment the longchain quaternary compound has at least one chain containing 6 or moreand more preferably 12 or more carbon atoms, such as3-chloro-2-hydroxypropyl-dimethyldodecylammonium chloride (soldcommercially as QUAB(r) 342) or the epoxide form of such compound, 2,3epoxypropyldimethyldodecylammonium chloride.

In still another embodiment of the invention, the one or morehydrophobic reagents may be a combination of reagents, such as, forexample, a succinic anhydride and a long chain quaternary ammoniumcompound. A dialkylanhydride, such as stearyl anhydride, may also besuitable in the present invention.

In a further embodiment, the hydrophobic reagent has a molecular weightgreater than about 220. Preferably, the hydrophobic reagent has amolecular weight greater than about 250.

In certain preferred embodiments, the modified starch-basedpolysaccharide has a weight average molecular weight of below 200,000.In certain preferred embodiments, the modified starch-basedpolysaccharide has a weight average molecular weight of from about 1,000to 25,000 or 1,500 to 15,000 and more preferably about 3,000 to about10,000.

In addition to starch-based polysaccharides, other polysaccharides aresuitable for use in the present invention. Such polysaccharides may bederived from plant sources and those based on sugar-type repeat units.Some non-limiting examples of these polysaccharides are guar, xanthan,pectin, carrageenan, locust bean gum, and cellulose, including physicaland chemically modified derivatives of the above. In embodiments of theinvention, physical, chemical and enzymatic degradation of thesematerials may be necessary to reduce the molecular weight to the desiredrange to provide the viscosity for the desired application. Chemicalmodification can also be performed to provide additional functionalproperties (e.g., cationic, anionic or non-ionic) such as treatment withpropylene oxide (PO), ethylene oxide (EO), alkyl chlorides (alkylation)and esterification such as 3-chloro-2-hydroxypropyl-trimethylammoniumchloride, sodium tripolyphosphate, chloroacetic acid, epichlorohydrin,phosphorous oxychloride and the like.

Another non-limiting example of a SAC derived from post-polymerizationmodification of a polysaccharide includes:

Dextran (poly[α(1→6)-D-glucose]) modified with3-chloro-2-hydroxypropyllauryldimethylammonium chloride; and the like.

Other synthetic routes may include polymerization of amino acids and/orpost-polymerization modification of polyaminoacids to achieve a SAC ofthe present invention, as well as, post-polymerization modification ofhydrophilic polymers or amphiphilic polymers to achieve SACs of thepresent invention, and the like.

Applicants have discovered that the SACs of the present invention areuseful in producing significant amounts of foam. For example, applicantshave found certain polymers tested in accordance with the Polymer FoamTest of the present invention which have exhibited a Max Foam Volume ofleast about 200 mL. In certain preferred embodiments, the SACs of thepresent invention exhibit a Max Foam Volume of at least about 400 mL,more preferably at least about 500 mL, more preferably at least about600 mL, and even more preferably at least about 700 mL.

Foam Stability is also important to the user of personal care products,such as described herein, as this often indicates a substantive, richlather. Foam Stability of the SACs of this invention is measured as apercent of the foam decay of the Max Foam Volume after being undisturbedfor 1000 seconds. Foam Stability is therefore calculated as the FoamVolume after 1000 seconds divided by the Max Foam Volume. Foam Stabilitythat is about 15% or greater than the Max Foam Volume after 1000 secondsis considered within acceptable limits in accordance with the presentinvention. In an embodiment, the SACs of this invention have a foamstability of about 40% or greater than the Max Foam Volume after 1000seconds. In another embodiment, the SACs provide foam stability of about80% or greater than the Max Foam Volume after 1000 seconds. In yetanother embodiment, the SACs provide foam stability about 90% or greaterthan the Max Foam Volume after 1000 seconds.

Applicants have discovered unexpectedly that according to embodiments ofthe invention, certain SACs not only provide foam that develops quicklyand in high volume, but they are also useful in producing compositionshaving low irritation. According to certain preferred embodiments,applicants have discovered that SACs of the present invention mayprovide a PMOD % (measured in accord with the procedure described hereinbelow and shown in the Examples) of less than about 90%, more preferablyless than about 80%, more preferably less than about 50%, and morepreferably less than about 40%, and are therefore useful in producingcompositions having beneficially low irritation properties associatedtherewith.

As is described in U.S. Pat. No. 7,417,020, entitled, “COMPOSITIONSCOMPRISING LOW-DP POLYMERIZED SURFACTANTS AND METHODS OF USE THEREOF,”issued to Fevola et al., commonly assigned, and herein incorporated byreference in its entirety, PMOD % is calculated using the “averagemicelle hydrodynamic diameter d_(H),” a measure of average micelle size.The “fraction of micelles with d_(H)<9 nanometers (nm)” provides ameasurement of the degree of irritation that may result fromcompositions that include surfactants. Surfactant micelles are rarelymonodisperse in size and aggregation number (i.e., the average number ofmolecules of surfactant in a particular micelle). Instead, surfactantmicelles tend to exist as a population with distributions of sizes andaggregation numbers that give rise to micelle size distributionfunctions. The “fraction of micelles with d_(H)<9 nanometers (nm)” isthus a measure of the capability of providing a distribution of micellesthat, is “shifted” to favor larger micelles.

Any amounts of SACs suitable to produce micelle size distributions ofthe present invention may be combined according to the present methods.According to certain embodiments, the SAC is used in a concentrationfrom greater than about 0.1% to about 30% by weight of active SAC in thecomposition. Preferably, the SAC is in a concentration from about 0.5 toabout 20%, more preferably from about 1 to about 15%, even morepreferably from about 2 to about 10% of active SAC in the composition.In certain other preferred embodiments, the compositions of the presentinvention comprise from about 0.5 to about 15%, more preferably fromabout 3 to about 15% or from about 1.5% to about 10% active SAC in thecomposition.

Applicants have discovered unexpectedly that by combining asuperhydrophilic amphiphilic copolymer with a micellar thickener one canform a composition that has both low irritation and high amounts offlash foam thereby greatly enhancing the aesthetic appeal of thecomposition.

Applicants have noted a surprising ability of micellar thickeners tothicken a composition having a superhydrophilic amphiphilic copolymerand further allow the composition to quickly reduce viscosity upondilution with water.

Without wishing to be bound by theory, upon investigation of Applicant'sdiscovery, Applicants believe that the superhydrophilic amphiphiliccopolymer is readily incorporated at the molecular level into theworm-like micelles whose formation is encouraged by the micellarthickener. The “intermolecular thickening network” thereby created ishighly concentration sensitive, and thus, “breaks” readily upondilution, allowing strong flash foam performance. This ability todisrupt the network upon dilution is particularly important forcompositions which are reliant upon the superhydrophilic amphiphiliccopolymer to generate foam, since superhydrophilic amphiphiliccopolymers are larger and generally more slowly diffusing thanconventional surfactants. This lack of mobility would otherwise reducethe ability of the superhydrophilic amphiphilic copolymer to generateflash foam.

As defined herein, the term, “micellar thickener,” as will be readilyunderstood by one skilled in the art, refers to a polymer that meets oneor both of the two criteria described below. According to the firstcriteria, (I): the micellar thickener is a polymer that includes atleast three hydrophilic repeat units or superhydrophilic repeat units,and further includes two or more independent hydrophobic moieties, andwherein the polymer has a relatively low weight-average molecularweight, e.g., less than about 100,000, preferably less than about50,000, more preferably less than about 25,000, most preferably lessthan about 10,000. Preferred hydrophobic moieties include 10 or morecarbon atoms, more preferably from 12 to 30 carbon atoms, even morepreferably from 16 to 26 carbon atoms, and most preferably from 18 to 24carbon atoms. Micellar thickeners that meet criteria (I) are generallybelieved to be suitable for modifying the corona (periphery) ofsurfactant micelles and, for convenience will hereinafter be referred toas “corona thickeners.”

According to the second criteria, (II): the micellar thickener is amolecule that includes at least two non-ionic hydrophilic moieties; andincludes either (a) two or more hydrophobic moieties that have a carbonchain that comprises 8 or more carbon atoms; or (b) one or morehydrophobic moieties that have a carbon chain that comprises 12 or morecarbon atoms; and has a molecular weight less than about 5,000(daltons), preferably less than about 3,000, more preferably less thanabout 2,000, most preferably less than about 1500. Micellar thickenersthat meet criteria (II) are generally believed to be suitable formodifying the core (center) of surfactant micelles and, for conveniencewill hereinafter be referred to as “core thickeners.”

Hydrophilic moieties, hydrophilic repeat units and superhydrophilicrepeat units are defined above with respect to SACs. Preferredhydrophilic moieties include nonionics such as hydroxyl and ethyleneoxy.Preferred hydrophilic repeat units or superhydrophilic repeat unitssuitable for inclusion in the micellar thickener include ethyleneoxy,those repeat units derived from glycerol, glycidol, or glycerylcarbonate as well as those derived from hydrophilic and superhydrophilicethylenically unsaturated monomers (e.g., acrylamide,N,N-dimethylacrylamide, acrylic acid, sodium acrylate, and sodiumacryloyldimethyllaurate). Ethyleneoxy repeat units are particularlypreferred. The number of hydrophilic repeat units may be from about 3 toabout 1000, preferably from about 5 to about 500, more preferably fromabout 6 to about 400. Hydrophobic moieties are also defined above withrespect to SACs. Preferred hydrophobic moieties suitable for inclusionare linear or branched, saturated or unsaturated alkyl or arylalkylgroups. In another preferred embodiment, the hydrophobic moiety includesadjoining repeat units or “blocks” of, for example, oxypropylene or(N-alkylacrylamide)s such as (N-t-butylacrylamide). For embodiments inwhich the hydrophobic moiety includes such blocks, the number of repeatunits per block is preferably from about 3 to about 400, more preferablyfrom about 5 to about 200. By “independent hydrophobic moieties” it ismeant the hydrophobic moieties do not include any common atoms, i.e.,they are positioned on different portions of the micellar thickener. Ina preferred embodiment, the micellar thickener is non-ionic.

The micellar thickener may include one or more linking groups thatserve, for example, to covalently bond a hydrophobic moiety to ahydrophilic repeat unit. Suitable linking groups include esters,thioesters, dithioesters, carbonates, thiocarbonates, trithiocarbonates,ethers, thioethers, amides, thioamides, carbamates/urethanes andxanthates. Preferred linking groups are esters and ethers.

In certain preferred embodiments, the micellar thickener is a coronathickener, as defined above. Preferably, the independent hydrophobicmoieties of the corona thickener are terminal, i.e., the hydrophobicmoieties are each positioned at a separate end or terminus of differentbranches of the polymer.

The corona thickener may be of varying chemical configurations. Onesuitable configuration is a linear configuration, such as one that maybe defined by the structure below:

in which HRU is a hydrophobic repeat unit having h units of HRU permole; L and L′ are linking groups; and R₁ and R₂ are hydrophobicmoieties. In certain preferred embodiments, the corona thickener is alinear molecule of the above formula in which h is 3-1000, preferably5-500, more preferably 6-400, and more preferably 10-300.

A suitable example of a linear corona thickeners are a fatty aciddiesters of polyethylene glycol (PEG), represented by the structurebelow:

where L and L′ are ester linking groups and the HRU is ethyleneoxy. Oneparticular example of such a linear corona thickener in which R₁ and R₂are C₁₇H₃₅ and n=150 repeat units is PEG-150 Distearate.

Other suitable examples of linear corona thickener are fatty acid estersof an ethoxylated fatty alcohol, represented by the structure below:

where L is an ether linking group and L′ is an ester linking group andthe HRU is ethyleneoxy. One particular example of such a linear coronathickener in which R₁ is C₂₄H₄₉ and R₂ is C₂₁H₄₃ and n=200 repeat unitsis Decyltetradeceth-200 Behenate.

Another suitable corona thickener having a linear configuration is onein which the hydrophilic repeat unit combines multiple hydrophilicfunctionalities, such as a hydrophobically modified ethoxylated urethane(HEUR). An example of such a corona thickener is shown below:

One particular example of such a HEUR in which R₁ is saturated diphenylmethylene, R₂ is C₁₈H₃₇, and x=150 repeat units is a PEG-150/StearylAlcohol/SMDI Copolymer.

Yet another suitable corona thickener having a linear configuration isone in which the hydrophobic moieties comprise three or more C₃ orgreater alkoxy groups in sequence and the hydrophilic repeat unit repeatunit includes ethylene oxide, such as a PPO-PEO-PPO block copolymer. Anexample of such a corona thickener is shown below:

Other suitable configurations of the corona thickener are those that arebranched or star-shaped in configuration. By “branched or star shaped”it is meant that the polymer includes multiple segments, e.g., 4 or 5segments, such as those that extend from a common node structure. Thenode structure may be, but is not necessarily, a group of atoms thatdoes not meet the above requirements for a hydrophobic moiety or ahydrophilic repeat unit. In one embodiment, the node structure is abranched hydrocarbon such as a neopentyl group (having 4 segments) shownbelow

or a cyclic group such as a saccharide derived from fructose, glucose,galactose, mannose, glucosamine, mannuronic acid, guluronic acid ontowhich various functional groups have been reacted (an example of which,having 5 segments, is shown below).

At least two of the segments that extend from the node structure includea terminal hydrophobic moiety, such as a terminal hydrophobic moietythat is joined to the node structure by an HRU. In certain embodiments,between 2 and 4 of the segments that are joined to the node structureinclude a terminal hydrophobic moiety, such as may be joined to the nodestructure by an HRU. In certain other embodiments one or more of thesegments is a terminal HRU, e.g., one that is joined to the nodestructure, but does not form a bridge between the node structure and aterminal hydrophobic moiety.

Branched and star-shaped corona thickeners may include fatty acidpolyesters of ethoxylated moieties. Suitable examples include fatty acidpolyesters of ethoxylated polyglycerols. Other suitable examples includefatty acid polyesters of ethoxylated monosaccharides (e.g., fructose,glucose, galactose, mannose, glucosamine, mannuronic acid, guluronicacid). Fatty acid polyesters of ethoxylated glucosides are particularlypreferred. One particular suitable example of a fatty acid polyester ofan ethoxylated glucoside is a fatty acid diester of ethoxylated methylglucoside, as represented by the structure below:

in which 4 distinct hydrophilic segments (here, each are comprised ofethyleneoxy HRUs) are linked via ether linkages to a methyl glucosidenodal structure. Two of the ethyleneoxy segments are also linked via anester linking group to terminal fatty acid hydrophobic moieties. Thus,this particular corona thickener has 5 segments, two of these fiveinclude independent terminal hydrophobic moieties. Two of the remainingsegments are terminal HRUs joined to the node structure via an etherlinkage. One particular example of such a corona thickener is one inwhich the sum of the number of ethyleneoxy repeat units, w+x+y+z=119 andR₁ and R₂ are C₁₇H₃₃ (oleate), is PEG-120 Methyl Glucose Dioleate, soldcommercially as Antil 120 Plus by Evonik. Other examples of suitablematerials comprise ethoxylated methyl glucoside fatty acid esters of thestructure below:

An example of such a material includes PEG-120 Methyl Glucose Dioleate,where x+y=120, R₁=R₂=C₁₇H₃₃, sold commercially as Glucamate DOE-120 byLubrizol.

Another suitable fatty acid polyester of an ethoxylated glucoside is afatty acid triester of ethoxylated methyl glucoside, as represented bythe structure below:

in which 4 distinct hydrophilic segments (here, each are comprised ofHRUs) are linked via ether linkages to a methyl glucoside nodalstructure. Three of the polyethyleneoxy segments are also linked via anester linking group to terminal fatty acid hydrophobic moieties, and thefourth polyethyleneoxy segment terminates with a hydroxyl group. Thus,this particular corona thickener has 5 segments, three of these fiveinclude independent terminal hydrophobic moieties. One of the remainingsegments is a terminal HRU joined to the node structure via an etherlinkage. One particular example of such a corona thickener is one inwhich the sum of the number of ethyleneoxy repeat units, w+x+y+z=119 andR₁ and R₂ are C₁₇H₃₃ (oleate), is PEG-120 Methyl Glucose Trioleate.Other examples of suitable materials comprise fatty acid esters ofethoxylated methyl glucoside fatty acid esters of the formula below:

An example of such a material includes PEG-120 Methyl Glucose Trioleate,where x+y=120, R₁=R₂=R₃=C₁₇H₃₃, sold commercially as Glucamate LT byLubrizol.

Another suitable example of corona thickener having a branched (orstar-shaped) configuration is one having 4 segments. The 4 segments mayeach include an independent hydrophobic moiety. These may be joined tothe node structure via HRUs. An example of a branched or star shapedcorona thickener having 4 segments, a fatty acid polyester of a starshaped PEG, is represented by the structure below:

in which 4 distinct hydrophilic segments (here, each are comprised ofethyleneoxy repeat units) are linked via ether linkages to a nodalstructure. The nodal structure consists of a pentaerythritylfunctionality (i.e. a quaternary carbon atom having four pendant CH₂groups bonded thereto). All four of the polyethyleneoxy segments arealso linked via an ester linking group to terminal fatty acidhydrophobic moieties. One particular example of such a corona thickeneris one in which the sum of the number of ethyleneoxy repeat units,w+x+y+z=150 and R₁, R₂, R₃, and R₄ are C₁₇H₃₅, is PEG-150Pentaerythrytyl Tetrastearate.

Another suitable example of corona thickener having a star-shapedconfiguration is a PEO-PPO star block copolymer. A suitable structure isprovided below:

In the corona thickener shown above, N—R—N represents a nodal structurefrom which four segments emanate. R may be, for example an ethyl group,—CH₂CH₂—. Each branch includes an ethyleneoxy segment of x repeat unitsand terminates with a poly(oxypropylene) hydrophobic block.

In certain embodiments, the micellar thickener is a core thickener, asdefined above. In certain preferred embodiments, core thickeners have alinear configuration. Examples of core thickeners include those derivedfrom glycerol. One suitable example of a core thickener derived fromglycerol is a glyceryl fatty acid ester, such as those defined by thestructure below:

One particular example is glyceryl oleate, in which R=C₁₇H₃₃.

Another example of a branched core thickener derived from glycerol is apolyglycerol, such as polyglyceryl fatty acid esters, such as such asthose defined by the structure below in which one of the hydrophilicmoieties is positioned in an HRU:

One particular example is polyglyceryl-10 oleate where R=C₁₇H₃₃ and x=9(Polyaldo 10-1-O, available from Lonza Group LLC, Basel Switzerland).

Yet another example of suitable core thickeners include fatty acid monoand di-alkanolamides, such as those defined by the structure below:

One particular example is Lauramide DEA, where R=C₁₁H₂₃ andR₁=R₂=CH₂CH₂OH.

Yet another example of suitable core thickeners include fatty acidesters of sorbitan, such as those defined by the structure below:

One particular example is sorbitan sesquicaprylate (available as AntilSC from Evonik Industries AG Dusseldorf, Germany), where R=C₇H₁₅CO or Hwith average 1.5 mol C₇H₁₅CO per mol sorbitan.

Any amounts of micellar thickeners suitable to increase viscosity ofcompositions of the present invention may be combined according to thepresent methods. For example, micellar thickener may be included in anamount in the formulation sufficient to increase the viscosity of thecomposition at least about 100 (when tested according to the FormulationViscosity Test, described below), preferably sufficient to raise theviscosity at least about 200 cP, more preferably sufficient to raise theviscosity at least about 500 cP, even more preferably sufficient toraise the viscosity at least about at least about 1000 cP. The increasesin viscosity specified above are as when compared with a compositionwhich has water substituted for the micellar thickener.

According to certain embodiments, the micellar thickener is used in aconcentration from greater than about 0.1% to about 15% by weight ofactive micellar thickener in the composition. Preferably, the micellarthickener is in a concentration from about 0.1 to about 10%, morepreferably from about 0.1% to about 5%, even more preferably from about0.2% to about 4%, even more preferably from about 0.5% to about 4%, andmost preferably from about 1% to about 4% of active micellar thickenerin the composition.

Applicants have discovered unexpectedly that the compositions of thepresent invention tend to have unexpected flash foaming properties. Inparticular, applicants have tested compositions of the present inventionin accord with the Formulation Flash Foam Test described hereinbelow andhave measured the foam volume at 20 cycles and the Foam Generation Ratesassociated therewith. Applicants have discovered that certainembodiments of the present invention produce a foam volume at 20 cyclesof about 250 mL or greater. In certain more preferred embodiments, theembodiments exhibit a foam volume at 20 cycles of about 300 mL orgreater, more preferably about 350 mL or greater, more preferably about400 mL or greater, more preferably about 450 mL or greater, and morepreferably about 500 mL or greater. Applicants have discovered thatcertain embodiments of the present invention exhibit a Foam GenerationRate of about 9 mL/cycle or greater. In certain more preferredembodiments, the embodiments exhibit a Foam Generation Rate of about 10mL/cycle or greater, more preferably about 12 mL/cycle or greater, morepreferably about 14 mL/cycle or greater, more preferably about 16mL/cycle or greater, more preferably about 18 mL/cycle or greater, morepreferably about 20 mL/cycle or greater, and more preferably about 22mL/cycle or greater.

Compositions useful in the present invention may also include any of avariety of conventional polymerized surfactants that do not meet therequirements specified above in order to be specified as a SAC. Examplesof suitable conventional polymerized surfactants include those describedin U.S. Pat. No. 7,417,020, entitled, “COMPOSITIONS COMPRISING LOW-DPPOLYMERIZED SURFACTANTS AND METHODS OF USE THEREOF,” issued to Fevola etal.

Compositions useful in the present invention may also include any of avariety of monomeric surfactants. By “monomeric surfactants” it is meantany surface active agents that do not meet the definition of“polymerized surfactant” as defined above. The monomeric surfactants maybe anionic, nonionic, amphoteric or cationic, examples of which aredetailed below.

According to certain embodiments, suitable anionic surfactants includethose selected from the following classes of surfactants: alkylsulfates, alkyl ether sulfates, alkyl monoglyceryl ether sulfates, alkylsulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl ethersulfosuccinates, alkyl sulfosuccinamates, alkyl amidosulfosuccinates,alkyl carboxylates, alkyl amidoethercarboxylates, alkyl succinates,fatty acyl sarcosinates, fatty acyl amino acids, fatty acyl taurates,fatty alkyl sulfoacetates, alkyl phosphates, and mixtures of two or morethereof. Examples of certain preferred anionic surfactants include:

alkyl sulfates of the formula

R′—CH₂OSO₃X′;

alkyl ether sulfates of the formula

R′(OCH₂CH₂)_(v)OSO₃X′;

alkyl monoglyceryl ether sulfates of the formula

alkyl monoglyceride sulfates of the formula

alkyl monoglyceride sulfonates of the formula

alkyl sulfonates of the formula

R′—SO₃X′;

alkylaryl sulfonates of the formula

alkyl sulfosuccinates of the formula:

alkyl ether sulfosuccinates of the formula:

alkyl sulfosuccinamates of the formula:

alkyl amidosulfosuccinates of the formula

alkyl carboxylates of the formula:

R′—(OCH₂CH₂)_(W)—OCH₂CO₂X′;

alkyl amidoethercarboxylates of the formula:

alkyl succinates of the formula:

fatty acyl sarcosinates of the formula:

fatty acyl amino acids of the formula:

fatty acyl taurates of the formula:

fatty alkyl sulfoacetates of the formula:

alkyl phosphates of the formula:

wherein

-   -   R′ is an alkyl group having from about 7 to about 22, and        preferably from about 7 to about 16 carbon atoms,    -   R′₁ is an alkyl group having from about 1 to about 18, and        preferably from about 8 to about 14 carbon atoms,    -   R′₂ is a substituent of a natural or synthetic I-amino acid,    -   X′ is selected from the group consisting of alkali metal ions,        alkaline earth metal ions, ammonium ions, and ammonium ions        substituted with from about 1 to about 3 substituents, each of        the substituents may be the same or different and are selected        from the group consisting of alkyl groups having from 1 to 4        carbon atoms and hydroxyalkyl groups having from about 2 to        about 4 carbon atoms and    -   v is an integer from 1 to 6;    -   w is an integer from 0 to 20;        and mixtures thereof.

Any of a variety of nonionic surfactants are suitable for use in thepresent invention. Examples of suitable nonionic surfactants include,but are not limited to, fatty alcohol acid or amide ethoxylates,monoglyceride ethoxylates, sorbitan ester ethoxylates alkylpolyglycosides, mixtures thereof, and the like. Certain preferrednonionic surfactants include polyethyleneoxy derivatives of polyolesters, wherein the polyethyleneoxy derivative of polyol ester (1) isderived from (a) a fatty acid containing from about 8 to about 22, andpreferably from about 10 to about 14 carbon atoms, and (b) a polyolselected from sorbitol, sorbitan, glucose, α-methyl glucoside,polyglucose having an average of about 1 to about 3 glucose residues permolecule, glycerine, pentaerythritol and mixtures thereof, (2) containsan average of from about 10 to about 120, and preferably about 20 toabout 80 ethyleneoxy units; and (3) has an average of about 1 to about 3fatty acid residues per mole of polyethyleneoxy derivative of polyolester. Examples of such preferred polyethyleneoxy derivatives of polyolesters include, but are not limited to PEG-80 sorbitan laurate andPolysorbate 20. PEG-80 sorbitan laurate, which is a sorbitan monoesterof lauric acid ethoxylated with an average of about 80 moles of ethyleneoxide, is available commercially from Croda, Inc. of Edison, N.J. underthe tradename, “Atlas G-4280.” Polysorbate 20, which is the lauratemonoester of a mixture of sorbitol and sorbitol anhydrides condensedwith approximately 20 moles of ethylene oxide, is available commerciallyfrom Croda, Inc. of Edison, N.J. under the tradename “Tween 20.”

Another class of suitable nonionic surfactants includes long chain alkylglucosides or polyglucosides, which are the condensation products of (a)a long chain alcohol containing from about 6 to about 22, and preferablyfrom about 8 to about 14 carbon atoms, with (b) glucose or aglucose-containing polymer. Preferred alkyl glucosides comprise fromabout 1 to about 6 glucose residues per molecule of alkyl glucoside. Apreferred glucoside is decyl glucoside, which is the condensationproduct of decyl alcohol with a glucose polymer and is availablecommercially from Cognis Corporation of Ambler, Pa. under the tradename,“Plantaren 2000.”

Any of a variety of amphoteric surfactants are suitable for use in thepresent invention. As used herein, the term “amphoteric” shall mean: 1)molecules that contain both acidic and basic sites such as, for example,an amino acid containing both amino (basic) and acid (e.g., carboxylicacid, acidic) functional groups; or 2) zwitterionic molecules whichpossess both positive and negative charges within the same molecule. Thecharges of the latter may be either dependent on or independent of thepH of the composition. Examples of zwitterionic materials include, butare not limited to, alkyl betaines and amidoalkyl betaines. Theamphoteric surfactants are disclosed herein without a counter ion. Oneskilled in the art would readily recognize that under the pH conditionsof the compositions of the present invention, the amphoteric surfactantsare either electrically neutral by virtue of having balancing positiveand negative charges, or they have counter ions such as alkali metal,alkaline earth, or ammonium counter ions.

Examples of amphoteric surfactants suitable for use in the presentinvention include, but are not limited to, amphocarboxylates such asalkylamphoacetates (mono or di); alkyl betaines; amidoalkyl betaines;amidoalkyl sultaines; amphophosphates; phosphorylated imidazolines suchas phosphobetaines and pyrophosphobetaines; carboxyalkyl alkylpolyamines; alkylimino-dipropionates; alkylamphoglycinates (mono or di);alkylamphoproprionates (mono or di); N-alkyl β-aminoproprionic acids;alkylpolyamino carboxylates; and mixtures thereof.

Examples of suitable amphocarboxylate compounds include those of theformula:

A-CONH(CH₂)_(x)N⁺R₅R₆R₇

-   -   wherein        -   A is an alkyl or alkenyl group having from about 7 to about            21, e.g. from about 10 to about 16 carbon atoms;        -   x is an integer of from about 2 to about 6;        -   R₅ is hydrogen or a carboxyalkyl group containing from about            2 to about 3 carbon atoms;        -   R₆ is a hydroxyalkyl group containing from about 2 to about            3 carbon atoms or is a group of the formula:

R₈—O—(CH₂)_(n)CO₂ ⁻

-   -   -   -   wherein                -   R₈ is an alkylene group having from about 2 to about                    3 carbon atoms and n is 1 or 2; and

        -   R₇ is a carboxyalkyl group containing from about 2 to about            3 carbon atoms;

Examples of suitable alkyl betaines include those compounds of theformula

B—N⁺R₉R₁₀(CH₂)_(p)CO₂ ⁻

-   -   wherein        -   B is an alkyl or alkenyl group having from about 8 to about            22, e.g., from about 8 to about 16 carbon atoms;        -   R₉ and R₁₀ are each independently an alkyl or hydroxyalkyl            group having from about 1 to about 4 carbon atoms; and        -   p is 1 or 2.            A preferred betaine for use in the present invention is            lauryl betaine, available commercially from Albright &            Wilson, Ltd. of West Midlands, United Kingdom as “Empigen            BB/J.”

Examples of suitable amidoalkyl betaines include those compounds of theformula:

D-CO—NH(CH₂)_(q)—N⁺R₁₁R₁₂(CH₂)_(m)CO₂ ⁻

-   -   wherein        -   D is an alkyl or alkenyl group having from about 7 to about            21, e.g. from about 7 to about 15 carbon atoms;        -   R₁₁ and R₁₂ are each independently an alkyl or Hydroxyalkyl            group having from about 1 to about 4 carbon atoms;        -   q is an integer from about 2 to about 6; and m is 1 or 2.            One amidoalkyl betaine is cocamidopropyl betaine, available            commercially from Evonik Industries of Hopewell, Va. under            the tradename, “Tegobetaine L7.”

Examples of suitable amidoalkyl sultaines include those compounds of theformula

-   -   wherein        -   E is an alkyl or alkenyl group having from about 7 to about            21, e.g. from about 7 to about 15 carbon atoms;        -   R₁₄ and R₁₅ are each independently an alkyl, or hydroxyalkyl            group having from about 1 to about 4 carbon atoms;        -   r is an integer from about 2 to about 6; and        -   R₁₃ is an alkylene or hydroxyalkylene group having from            about 2 to about 3 carbon atoms;

In one embodiment, the amidoalkyl sultaine is cocamidopropylhydroxysultaine, available commercially from Rhodia Novecare ofCranbury, N.J. under the tradename, “Mirataine CBS.”

Examples of suitable amphophosphate compounds include those of theformula:

-   -   wherein        -   G is an alkyl or alkenyl group having about 7 to about 21,            e.g. from about 7 to about 15 carbon atoms;        -   s is an integer from about 2 to about 6;        -   R₁₆ is hydrogen or a carboxyalkyl group containing from            about 2 to about 3 carbon atoms;        -   R₁₇ is a hydroxyalkyl group containing from about 2 to about            3 carbon atoms or a group of the formula:

R₁₉—O—(CH₂)_(t)—CO₂ ⁻

-   -   -   -   wherein                -   R₁₉ is an alkylene or hydroxyalkylene group having                    from about 2 to about 3 carbon atoms and                -   t is 1 or 2; and

        -   R₁₈ is an alkylene or hydroxyalkylene group having from            about 2 to about 3 carbon atoms.

In one embodiment, the amphophosphate compounds are sodium lauroamphoPG-acetate phosphate, available commercially from Croda, Inc. of Edison,N.J. under the tradename, “Monateric 1023,” and those disclosed in U.S.Pat. No. 4,380,637, which is incorporated herein by reference.

Examples of suitable phosphobetaines include those compounds of theformula:

wherein E, r, R₁, R₂ and R₃, are as defined above. In one embodiment,the phosphobetaine compounds are those disclosed in U.S. Pat. Nos.4,215,064, 4,617,414, and 4,233,192, which are all incorporated hereinby reference.

Examples of suitable pyrophosphobetaines include those compounds of theformula:

wherein E, r, R₁, R₂ and R₃, are as defined above. In one embodiment,the pyrophosphobetaine compounds are those disclosed in U.S. Pat. Nos.4,382,036, 4,372,869, and 4,617,414, which are all incorporated hereinby reference.

Examples of suitable carboxyalkyl alkylpolyamines include those of theformula:

-   -   wherein        -   I is an alkyl or alkenyl group containing from about 8 to            about 22, e.g. from about 8 to about 16 carbon atoms;        -   R₂₂ is a carboxyalkyl group having from about 2 to about 3            carbon atoms;        -   R₂₁ is an alkylene group having from about 2 to about 3            carbon atoms and        -   u is an integer from about 1 to about 4.

Classes of cationic surfactants that are suitable for use in thisinvention include alkyl quaternaries (mono, di, or tri), benzylquaternaries, ester quaternaries, ethoxylated quaternaries, alkylamines, and mixtures thereof, wherein the alkyl group has from about 6carbon atoms to about 30 carbon atoms, with about 8 to about 22 carbonatoms being preferred.

Any amounts of monomeric surfactant suitable to produce low smallmicelle fraction composition may be combined according to the presentmethods. For example, the amount of monomeric surfactants used in thepresent invention may be from about 0.1 to about 30%, more preferablyfrom about 0.5 to about 20%, even more preferably from about 1 to about15% of total active monomeric surfactant in the composition, and evenmore preferably from about 2% to about 10%.

Any relative amounts of polymerized surfactants and monomeric surfactantsuitable to produce low small micelle fraction composition may becombined according to the present methods. According to certainembodiments, the compositions comprise a ratio of SAC to the sum totalof all monomeric surfactants of from about 0.1:1 to about 5:1, andpreferably from about 0.25:1 to about 3:1.

The compositions of the present invention may comprise any of a varietyof additional other ingredients used conventionally inhealthcare/personal care compositions (“personal care components”).These other ingredients nonexclusively include one or more, pearlescentor opacifying agents, thickening agents, emollients, secondaryconditioners, humectants, chelating agents, actives, exfoliants, andadditives which enhance the appearance, feel and fragrance of thecompositions, such as colorants, fragrances, preservatives, pH adjustingagents, and the like.

Any of a variety of commercially available pearlescent or opacifyingagents which are capable of suspending water insoluble additives such assilicones and/or which tend to indicate to consumers that the resultantproduct is a conditioning shampoo are suitable for use in thisinvention. The pearlescent or opacifying agent may be present in anamount, based upon the total weight of the composition, of from about 1percent to about 10 percent, e.g. from about 1.5 percent to about 7percent or from about 2 percent to about 5 percent. Examples of suitablepearlescent or opacifying agents include, but are not limited to mono ordiesters of (a) fatty acids having from about 16 to about 22 carbonatoms and (b) either ethylene or propylene glycol; mono or diesters of(a) fatty acids having from about 16 to about 22 carbon atoms (b) apolyalkylene glycol of the formula: HO-(JO)_(a)—H, wherein J is analkylene group having from about 2 to about 3 carbon atoms; and a is 2or 3; fatty alcohols containing from about 16 to about 22 carbon atoms;fatty esters of the formula: KCOOCH₂L, wherein K and L independentlycontain from about 15 to about 21 carbon atoms; inorganic solidsinsoluble in the shampoo composition, and mixtures thereof.

The pearlescent or opacifying agent may be introduced to the mildcleansing composition as a pre-formed, stabilized aqueous dispersion,such as that commercially available from Cognis Corporation of Ambler,Pa. under the tradename, “Euperlan PK-3000.” This material is acombination of glycol distearate (the diester of ethylene glycol andstearic acid), Laureth-4 (CH₃(CH₂)₁₀CH₂(OCH₂CH₂)₄OH) and cocamidopropylbetaine and may be in a weight percent ratio of from about 25 to about30:about 3 to about 15:about 20 to about 25, respectively.

Compositions useful in the present invention may also include any of avariety of conventional thickeners that do not meet the requirementsspecified above in order to be considered micellar thickeners. Examplesof suitable conventional thickeners include various thickeners havingmolecular weights of greater than about 100,000 grams per mole,including chemistries such as: hydroxyalkyl cellulose; alkyl cellulose;hydroxyalkyl alkyl cellulose; xanthan and guar gums, succinoglycan gums;and mixtures thereof.

Examples of suitable thickening agents nonexclusively include: mono ordiesters of 1) polyethylene glycol of formula: HO—(CH₂CH₂O)_(z)H,wherein z is an integer from about 3 to about 200; and 2) fatty acidscontaining from about 16 to about 22 carbon atoms; fatty acid esters ofethoxylated polyols; ethoxylated derivatives of mono and diesters offatty acids and glycerine; hydroxyalkyl cellulose; alkyl cellulose;hydroxyalkyl alkyl cellulose; hydrophobically-modified alkali swellableemulsions (HASEs); hydrophobically-modified ethoxylated urethanes(HEURs); xanthan and guar gums; and mixtures thereof. Preferredthickeners include polyethylene glycol ester, and more preferablyPEG-150 distearate which is available from the Hallstar Company ofChicago, Ill. under the tradename, “PEG 6000 DS”.

Any of a variety of commercially available secondary conditioners, suchas volatile silicones, which impart additional attributes, such as glossto the hair are suitable for use in this invention. The volatilesilicone conditioning agent has an atmospheric pressure boiling pointless than about 220° C. The volatile silicone conditioner may be presentin an amount of from about 0 percent to about 3 percent, e.g. from about0.25 percent to about 2.5 percent or from about 0.5 percent to about 1.0percent, based on the overall weight of the composition. Examples ofsuitable volatile silicones nonexclusively include polydimethylsiloxane,polydimethylcyclosiloxane, hexamethyldisiloxane, cyclomethicone fluidssuch as polydimethylcyclosiloxane available commercially from DowCorning Corporation of Midland, Mich. under the tradename, “DC-345” andmixtures thereof, and preferably include cyclomethicone fluids. Othersuitable secondary conditioners include cationic polymers, includingpolyquarterniums, cationic guar, and the like.

Any of a variety of commercially available humectants, which are capableof providing moisturization and conditioning properties to the personalcleansing composition, are suitable for use in the present invention.The humectant may be present in an amount of from about 0 percent toabout 10 percent, e.g. from about 0.5 percent to about 5 percent or fromabout 0.5 percent to about 3 percent, based on the overall weight of thecomposition. Examples of suitable humectants nonexclusively include: 1)water soluble liquid polyols selected from the group comprisingglycerine, propylene glycol, hexylene glycol, butylene glycol,dipropylene glycol, polyglycerols, and mixtures thereof; 2) polyalkyleneglycol of the formula: HO—(R″O)_(b)—H, wherein R″ is an alkylene grouphaving from about 2 to about 3 carbon atoms and b is an integer of fromabout 2 to about 10; 3) polyethylene glycol ether of methyl glucose offormula CH₃—C₆H₁₀O₅—(OCH₂CH₂)_(c)—OH, wherein c is an integer from about5 to about 25; 4) urea; and 5) mixtures thereof, with glycerine beingthe preferred humectant.

Examples of suitable chelating agents include those which are capable ofprotecting and preserving the compositions of this invention.Preferably, the chelating agent is ethylenediamine tetracetic acid(“EDTA”), and more preferably is tetrasodium EDTA, availablecommercially from Dow Chemical Company of Midland, Mich. under thetradename, “Versene 100XL” and is present in an amount, based upon thetotal weight of the composition, from about 0 to about 0.5 percent orfrom about 0.05 percent to about 0.25 percent.

Suitable preservatives include, for example, parabens, quaternaryammonium species, phenoxyethanol, benzoates, DMDM hydantoin, and arepresent in the composition in an amount, based upon the total weight ofthe composition, from about 0 to about 1 percent or from about 0.05percent to about 0.5 percent.

The SAC, optional micellar thickener, and optional monomeric surfactantsand optional other components of the composition may be combinedaccording to the present invention via any conventional methods ofcombining two or more fluids or solids. For example, one or morecompositions comprising, consisting essentially of, or consisting of atleast one SAC and one or more compositions comprising, consistingessentially of, or consisting of water, monomeric surfactants orsuitable ingredients may be combined by pouring, mixing, addingdropwise, pipetting, pumping, and the like, one of the compositionscomprising the polymerized surfactant into or with the other in anyorder using any conventional equipment such as a mechanically stirredpropeller, paddle, and the like.

The methods of the present invention may further comprise any of avariety of steps for mixing or introducing one or more of the optionalcomponents described hereinabove with or into a composition comprising aSAC either before, after, or simultaneously with the combining stepdescribed above. While in certain embodiments, the order of mixing isnot critical, it is preferable, in other embodiments, to pre-blendcertain components, such as the fragrance and the nonionic surfactantbefore adding such components into a composition comprising thepolymerized surfactant.

The pH of the present compositions is not critical, but may be in arange that does not facilitate irritation to the skin, such as fromabout 4 to about 7. The viscosity of the personal care composition isnot critical, although it may be a spreadable cream or lotion or gel. Incertain embodiments, the personal care composition has a viscosity fromabout 200 cP to about 10,000 cP, such as when evaluated according to theFormulation Viscosity Test, as described below.

The compositions may be made into a wide variety of product types thatinclude but are not limited to cleansing liquid washes, gels, sticks,sprays, solid bars, shampoos, pastes, foams, powders, mousses, shavingcreams, wipes, patches, nail lacquers, wound dressing and adhesivebandages, hydrogels, films and make-up such as foundations, mascaras,and lipsticks. These product types may comprise several types ofcarriers including, but not limited to solutions, emulsions (e.g.,microemulsions and nanoemulsions), gels, and solids. Other carriersinclude solvents, which can include, but are not limited to water,acetone, alcohols, such as isopropanol and ethanol, ethylene glycol,glycerin, dimethylformamide, tetrahydrofuran, dimethylsulfoxide,sorbitol and ethers and ester of sorbitol. In an embodiment of theinvention, water and alcohols are the preferred carriers. Other carrierscan be formulated by those of ordinary skill in the art.

The compositions useful in the present invention may includeformulations suitable for administering to the target tissues, such ashuman skin. In one embodiment, the composition comprises asuperhydrophilic amphiphilic copolymer and a carrier, preferably acosmetically-acceptable carrier. As used herein, the term“cosmetically-acceptable carrier” means a carrier that is suitable foruse in contact with the skin without undue toxicity, incompatibility,instability, irritation, allergic response, and the like. Thecompositions can be formulated as solutions. Solutions typically includean aqueous or organic solvent (e.g., from about 50% to about 99.99% orfrom about 90% to about 99% of a cosmetically acceptable aqueous ororganic solvent). Examples of suitable organic solvents include:polyglycerols, propylene glycol, polyethylene glycol (200, 600),polypropylene glycol (425, 2025), glycerol, 1,2,4-butanetriol, sorbitolesters, 1,2,6-hexanetriol, ethanol, and mixtures thereof. In certainpreferred embodiments, the compositions of the present invention areaqueous solutions comprising from about 50% to about 99% by weight ofwater.

According to certain embodiments, compositions useful in the subjectinvention may be formulated as a solution comprising an emollient. Suchcompositions preferably contain from about 2% to about 50% of anemollient(s). As used herein, “emollients” refer to materials used forthe prevention or relief of dryness, as well as for the protection ofthe skin. A wide variety of suitable emollients are known and may beused herein. Sagarin, Cosmetics, Science and Technology, 2nd Edition,Vol. 1, pp. 32 43 (1972) and the International Cosmetic IngredientDictionary and Handbook, eds. Wenninger and McEwen, pp. 1656 61, 1626,and 1654 55 (The Cosmetic, Toiletry, and Fragrance Assoc., Washington,D.C., 7.sup.th Edition, 1997) (hereinafter “ICI Handbook”) containsnumerous examples of suitable materials. A lotion can be made from sucha solution. Lotions typically comprise from about 1% to about 20% (e.g.,from about 5% to about 10%) of an emollient(s) and from about 50% toabout 90% (e.g., from about 60% to about 80%) of water.

The present compositions may be of varying phase compositions, but arepreferably aqueous solutions or otherwise include an exterior aqueousphase (e.g., aqueous phase is the most exterior phase of thecomposition). As such, compositions of the present invention may beformulated to be oil-in-water emulsions that are shelf-stable in thatthe emulsion does not lose phase stability or “break” when kept atstandard conditions (22 degrees Celsius, 50% relative humidity) for aweek or more after it is made.

In certain embodiments, the compositions produced via the presentinvention are preferably used as or in personal care products fortreating or cleansing at least a portion of a human body. Examples ofcertain preferred personal care products include various productssuitable for application to the skin, hair, oral and/or perineal regionof the body, such as shampoos, hand, face, and/or body washes, bathadditives, gels, lotions, creams, and the like. As discussed above,applicants have discovered unexpectedly that the instant methods providepersonal care products having reduced irritation to the skin and/or eyesand, in certain embodiments one or more of desirable properties such asflash foaming characteristics, rheology, and functionality, even at highsurfactant concentrations. Such products may further include a substrateonto which a composition is applied for use on the body. Examples ofsuitable substrates include a wipe, pouf, sponge, and the like as wellas absorbent articles, such as a bandage, sanitary napkin, tampon, andthe like.

The present invention provides methods of treating and/or cleansing thehuman body comprising contacting at least a portion of the body with acomposition of the present invention. Certain preferred methodscomprising contacting mammalian skin, hair and/or vaginal region with acomposition of the present invention to cleanse such region and/or treatsuch region for any of a variety of conditions including, but notlimited to, acne, wrinkles, dermatitis, dryness, muscle pain, itch, andthe like. Any of a variety of actives or benefit agents known in the artfor treating such conditions may be used in the present invention.

What is meant by a “benefit agent” is an element, an ion, a compound(e.g., a synthetic compound or a compound isolated from a naturalsource) or other chemical moiety in solid (e.g. particulate), liquid, orgaseous state and compound that has a cosmetic or therapeutic effect onthe skin.

The compositions of the present invention may further include one ormore benefit agents or pharmaceutically-acceptable salts and/or estersthereof, the benefit agents generally capable of interacting with theskin to provide a benefit thereto. As used herein, the term “benefitagent” includes any active ingredient that is to be delivered intoand/or onto the skin at a desired location, such as a cosmetic orpharmaceutical.

The benefit agents useful herein may be categorized by their therapeuticbenefit or their postulated mode of action. However, it is to beunderstood that the benefit agents useful herein may, in somecircumstances, provide more than one therapeutic benefit or operate viagreater than one mode of action. Therefore, the particularclassifications provided herein are made for the sake of convenience andare not intended to limit the benefit agents to the particularapplication(s) listed.

Examples of suitable benefit agents include those that provide benefitsto the skin, such as, but not limited to, depigmentation agents;reflectants; amino acids and their derivatives; antimicrobial agents;allergy inhibitors; anti-acne agents; anti-aging agents; anti-wrinklingagents, antiseptics; analgesics; shine-control agents; antipruritics;local anesthetics; anti-hair loss agents; hair growth promoting agents;hair growth inhibitor agents, antihistamines; antiinfectives;anti-inflammatory agents; anticholinergics; vasoconstrictors;vasodilators; wound healing promoters; peptides, polypeptides andproteins; deodorants and anti-perspirants; medicament agents; skinfirming agents, vitamins; skin lightening agents; skin darkening agents;antifungals; depilating agents; counterirritants; hemorrhoidals;insecticides; enzymes for exfoliation or other functional benefits;enzyme inhibitors; poison ivy products; poison oak products; burnproducts; anti-diaper rash agents; prickly heat agents; vitamins; herbalextracts; vitamin A and its derivatives; flavonoids; sensates;anti-oxidants; hair lighteners; sunscreens; anti-edema agents,neo-collagen enhancers, film-forming polymers, chelating agents;anti-dandruff/sebhorreic dermatitis/psoriasis agents; keratolytics; andmixtures thereof.

The cleansing methods of the present invention may further comprise anyof a variety of additional, optional steps associated conventionallywith cleansing hair and skin including, for example, lathering, rinsingsteps, and the like.

As noted above, the SACs of the present invention are particularlyadvantageous in healthcare applications. However, the SACs also haveapplication in non-healthcare applications, for example in industrialuses. Non-limiting examples of such applications include detergentapplications, anti-scale applications, such as autodish, emulsificationof oils and tars, foam boosting for reducing the density and aeratingporous materials, cleansing of fabrics or industrial surfaces, as asurface tension modifier for coating applications, providing foamingand/or cleaning for applications that require biodegradable components,and the like.

In embodiments of the invention comprising compositions that include theSACs of this invention, the compositions may include functionalmaterials to enhance performance in each particular application. Someexamples of these functional materials are: surfactants, anti-scalepolymers, chelating agents, viscosity modifiers, antioxidants, colloidalstabilizers and anti-re-deposition polymers. The SACs of this inventioncan also be used to reduce the density of and provide porosity within asolid article, in which in these applications the SAC will be used inconjunction with a structural material. Such structural materials caninclude activated charcoal, absorbent materials, such as polyacrylicacid, structural materials such as cellulose, polyvinyl alcohol,polystyrene and polyacrylates and copolymers of these. The above listillustrates the broad uses of a foam stabilizing SAC and is not meant tolimit the scope of this invention.

EXAMPLES

The following Drop Shape Analysis (“DSA”), Dynamic Light Scattering(“DLS”), Polymer Foam, Formulation Foam, Solution Viscosity, FormulationFlash Foam, and Formulation Viscosity tests are used in the instantmethods and in the following Examples. In particular, as describedabove, the DSA test is used to determine the degree to which a polymericmaterial (e.g. a SAC) in a composition reduces surface tension,according to the present invention; the DLS test, Polymer Foam Test, andSolution Viscosity may be used to determine the suitability of aparticular SAC to provide reduced irritation and high foam; and theFormulation Flash Foam Test and Formulation Viscosity tests may be usedto determine degree to which a particular composition can generate highfoam, and/or provide beneficial viscosity, which is often desirable forcleansing compositions.

Unless otherwise indicated, the amounts of ingredients in the Exampleand Comparative compositions listed in the tables are expressed in w/w %of ingredient based on the total composition.

Drop Shape Analysis Test (“DSA Test”)

Dynamic surface tension reduction is determined via the DSA Test. DropShape Analysis (DSA, also known as Pendant prop Method or PDM) is awell-known method for measuring the static interfacial or surfacetension (γ) as a function of time. The surface tension measured by DSAis determined by fitting the shape of the hanging drop (captured in avideo image) to the Young-Laplace equation, which relates inter-facialtension to drop shape. The Laplace equation is the mechanicalequilibrium condition for two homogeneous fluids separated by aninterface (Handbook of Applied Surface and Colloid Chemistry, Vol. 2;Holmberg, K., Ed.; John Wiley & Sons: Chicester, U.K., 2002, pp222-223). It relates the pressure difference across a curved interfaceto the surface tension and the curvature of the interface:

$\begin{matrix}{{\gamma \left( {\frac{1}{R_{1}} + \frac{1}{R_{2}}} \right)} = {\Delta \; P}} & (1)\end{matrix}$

where R₁ and R₂ are the two principal radii of curvature, and ΔP is thepressure difference across the interface. In the absence of any externalforces other than gravity (g), ΔP may be expressed as a linear functionof the elevation:

ΔP=ΔP ₀+(Δp)gz  (2)

where ΔP₀ is the pressure difference at a reference plane and z is thevertical coordinate of the drop measured from the reference plane. Thusfor a given value of γ, the shape of a drop may be determined (refer toLahooti S., del Río O. I., Cheng P., Neumann A. W. In Axisymmetric DropShape Analysis (ADSA), Neumann A. W., Spelt J. K., Eds. New York: MarcelDekker Inc., 1996, Ch. 10; Hoorfar M., Neumann, A. W. Adv. Coll. andInterface Sci., 2006, 121(1-3), 25-49).

Solutions for the determination of surface tension were prepared asfollows: a polymer sample (1150 mg active solids) is diluted inMillipore-Q deionized water (200 mL) in an acid-washed glass flask withglass stopper. This stock solution is mixed by manually shaking for fiveminutes and allowed to stand overnight. A dilution (¼) of the stocksolution is prepared by further diluting the stock solution withMillipore-Q water in acid-washed glassware—this is the sample is usedfor DSA analysis.

The samples are analyzed using a DSA 100 instrument (Krüss GmbH,Hamburg, Germany) operating at 25.0° C. The drop was monitored over 120seconds and images were captured approximately every 0.16 seconds forthe first 10 seconds, every 0.5 seconds for the next 50 seconds, andevery second for the last 60 seconds. All of the captured images areanalyzed to determine the surface tension at each time frame. Surfacetension values are calculated using the prop Shape Analysis (DSA) forWindows™ package (Krüss GmbH, Hamburg, Germany). Dynamic reduction ofsurface tension is reported as the time in seconds required to reducethe surface tension of the test solution to 55 mN/m, t_(γ=55). Thereported values of t_(γ=55) are the average of three individualmeasurement runs.

Solution Viscosity Test:

Solution viscosities of solutions of test material (e.g., SACs), 2 wt %in DI water were conducted on a controlled-stress rheometer (AR-2000, TAInstruments Ltd., New Castle, Del., USA). Steady-state shear stresssweeps were performed at 25.0±0.1° C. using a double-wall Couettegeometry. Data acquisition and analysis were performed with the RheologyAdvantage software v4.1.10 (TA Instruments Ltd., New Castle, Del., USA).Zero-shear apparent viscosities for Newtonian fluids are reported as theaverage of viscosity values obtained over a range of shear stresses(0.02-1.0 Pa). For pseudoplastic (shear-thinning) fluids, zero-shearapparent viscosities were calculated via the fitting of shear stresssweep data to an Ellis viscosity model.

Polymer Foam Test:

The following Polymer Foam Test was performed on various test materials(e.g., polymerized surfactant) to determine the foam volume uponagitation according to the present invention. The Polymer Foam Test isconducted as follows: a solution of the test material (1000 mL of a 0.5wt % solution) is first prepared according to the following procedure:900 g deionized (DI) water is charged to an appropriately sized glassbeaker equipped with a mechanical stirrer and hotplate. While mixing atlow to medium speeds and heating to 75-80° C., the polymer sample (5.0 gactive solids) is slowly added to the beaker. The polymer solution isallowed to mix at 75-80° C. for 15 min, or until the polymer iscompletely dissolved, at which point heating is ceased and the solutionallowed to begin cooling to ambient temperature. When the batchtemperature falls below 40° C., DMDM Hydantoin (3.0 g of a 55 wt %solution, sold as Glydant from Lonza) and Tetrasodium EDTA (5.0 g of a50 wt % solution, sold as Versene XL from Dow Chemical) are added to thesolution. The solution pH is adjusted to pH=7.0±0.2 using 20 wt % SodiumHydroxide solution and/or 20 wt % Citric Acid solution, followed by theaddition of DI water in q.s. to 100 wt %. The polymer solution isallowed to cool to ambient temperature and stored in a sealed glass jaruntil ready for use. To determine the Maximum Foam Volume, the polymersolution (1000 mL) was added to the sample tank of a Sita R-2000 foamtester (commercially available from Future Digital Scientific, Co.;Bethpage, N.Y.). The test parameters were set to repeat three runs(series count=3) of 250 ml sample size (fill volume=250 ml) withthirteen stir cycles (stir count=13) for a 15 second stir time per cycle(stir time=15 seconds) with the rotor spinning at 1200 RPM(revolution=1200) at a temperature setting of 30° C.±2° C. Foam Volumedata was collected at the end of each stir cycle and the average andstandard deviation of the three runs was determined. The Maximum FoamVolume was reported for each Example as the value after the thirteenthstir cycle.

Formulation Foam Test:

The following Formulation Foam Test was performed on various personalcare compositions to determine the foam volume upon agitation accordingto the present invention. First, a solution of the test composition isprepared in simulated tap water. To represent the hardness of tap water,0.36 g of calcium chloride is dissolved in 995 g of DI water. Five (5.0)grams of test composition is then added to this solution and mixed untilhomogeneous. To determine the Formulation Foam Volume, the composition(1000 mL) was added to the sample tank of a Sita R-2000 foam tester(commercially available from Future Digital Scientific, Co.; Bethpage,N.Y.). The test parameters were set to repeat three runs (seriescount=3) of 250 ml sample size (fill volume=250 ml) with thirteen stircycles (stir count=13) for a 15 second stir time per cycle (stir time=15seconds) with the rotor spinning at 1200 RPM (revolution=1200) at atemperature setting of 30° C.±2° C. Foam volume data was collected atthe end of each stir cycle and the average and standard deviation of thethree runs was determined. The Formulation Foam was reported for eachExample as the value after the thirteenth stir cycle.

Dynamic Light Scattering Test (“DLS Test”):

Dynamic light scattering (DLS, also known as Photon CorrelationSpectroscopy or PCS) is a well-known method for determination of averagemicelle size (measured as hydrodynamic diameter, d_(H)) and micelle sizedistribution (A comprehensive explanation of the technique can be foundin the ISO test method ISO013321:1996(E). The hydrodynamic size measuredby DLS is defined as the size of a hypothetical hard sphere thatdiffuses in the same fashion as that of the particle being measured. Inpractice, micellar species are dynamic (tumbling), solvated species thatmay be isotropic (spherical) or anisotropic (e.g. ellipsoidal orcylindrical) in shape. Because of this, the diameter calculated from thediffusion properties of the micelle will be indicative of the apparentsize of the dynamic hydrated/solvated particle; hence the terminology,“hydrodynamic diameter.” Micellar solutions for determination of micelled_(H) are prepared by diluting the compositions to 3.0% of theiroriginal concentration with 0.1 μm-filtered deionized water, obtainedfrom a Millipore-Q filtration system. (The target dilution of 3.0% ischosen because it is within the typical concentration range of 1.0%-10%dilution that is encountered during the use of rinse-off personal carecompositions. The target dilution is also within the range of dilutionsemployed in the TEP test.) The samples are agitated on a vortex mixer at1000 rpm for a minimum of five minutes and then allowed to standovernight prior to analysis. Samples are passed through a 0.2 μm Anatop-Plus syringe filter into dust-free disposable acrylic sizingcuvettes and sealed.

The samples are analyzed using a Zetasizer Nano ZS DLS instrument(Malvern Instruments, Inc., Southborough, Mass.) operating at 25.0° C.Samples must yield a minimum count rate of 100,000 counts per second(cps) for accurate determination of micelle d_(H) and micelle sizedistribution. For samples with count rates below this minimum, thesample concentration may be gradually increased (i.e. diluted less)until the minimum count rate is achieved, or in some cases, the samplemay be run in neat form. Values of micelle d_(H) and the micelle sizedistribution are calculated using the Dispersion Technology Software(DTS) v4.10 package (Malvern Instruments Inc., Southborough, Mass.),which calculates the Z-average micelle d_(H) according to the ISO13321test method. Values of average micelle d_(H) are reported herein as theZ-average micelle d_(H). The reported values of micelle d_(H) are theaverage of three individual measurement runs. The intensity distributionof micelle size calculated by the DTS software is used to calculate thefraction of micelles having values of d_(H) under a given size limit.

Additives exhibiting relatively large values of d_(H) (i.e. greater thanabout 200 nm) compared to micellar species, for example, high MWpolymeric rheology modifiers, polymeric conditioners, particulateopacifiers, (micro)emulsions of hydrophobic emollients, silicone(micro)emulsions, etc., are routinely added to personal carecompositions comprising micellar species. To those skilled in the art ofDLS, it is apparent that such nonmicellar materials will exhibit lightscattering intensities orders of magnitude greater than the relativelysmaller micellar species in the diluted sample. The scattering intensityof such materials will overwhelm the scattering signal of the micellarspecies, thus interfering in the accurate determination of micelled_(H). Typically, this type of interference will lead to an erroneouslylarge measured value of micelle d_(H). To avoid such interference, it ismost preferable to measure the micelle d_(H) of the composition in theabsence of additives exhibiting values of d_(H) greater than about 200nm. Those skilled in the art of DLS will recognize that additivesexhibiting large values of d_(H) should be separated from the sample viafiltration or ultracentrifugation prior to determination of the micelled_(H) of the sample. Alternatively, higher order analysis of the DLSdata using the Dispersion Technology Software v4.10 package may also beemployed to obtain enhanced resolution and properly characterize micelled_(H) in the presence of nonmicellar scattering species.

In accord with the above description and as shown hereafter in theExamples, the “PMOD %” and “PMODz-average” associated with a testmaterial (e.g., polymerized surfactant) are calculated by preparing amodel composition comprising about 4.8 active weight % of the testmaterial, 0.3 weight percent of a combination of sodium methyl- (and)sodium propyl- (and) sodium ethyl paraben, (such as the productcommercially available as Nipasept Sodium), 0.25 weight percent oftetrasodium EDTA (such as Versene 100 XL), with q.s. water, and usingthe DLS test to measure the fraction of micelles having a dH of lessthan 9 nm in the resulting model composition (PMOD %), and the z-averagemicelle dH associated therewith (PMODz-average). Applicants haverecognized that in certain embodiments, the test material may beincompatible with the above model composition. Thus, if, and only if,the formulation of the above model composition results in two separateliquid phases and/or precipitation of the polymer surfactant, then thePMOD % and PMODz-average procedure comprises making a compositioncomprising about 4.8 active weight % of the test material, 0.5 weightpercent of sodium benzoate, 0.25 weight percent of tetrasodium EDTA(such as Versene 100 XL), with q.s. citric acid to a pH of 4.8±0.2, withq.s. water, and using the DLS test to measure the fraction of micelleshaving a d_(H) of less than 9 nm in the resulting model composition(PMOD %), and the z-average micelle d_(H) associated therewith(PMODz-average).

Formulation Viscosity Test:

The following Viscosity Test was performed on various personal carecompositions to determine the viscosity according to the presentinvention. Viscosities of test formulations were conducted at 25° C.using a Brookfield DV-I+ viscometer (Brookfield EngineeringLaboratories, Inc. Middleboro, Mass.). Measurement parameters areselected so as to ensure “% torque” is between 40%-60% on theviscometer. Typical operating parameters are spindle #S62 operating atsix rpm. One skilled in the art will recognize that in order toaccommodate samples of higher viscosities, it may be necessary to changespindle selection or operating speed to enable a viscosity measurement.

Formulation Flash Foam Test:

The following Formulation Flash Foam Test was performed on variouspersonal care compositions to determine the foam volume as a function ofagitation, according to the present invention. To a bottom of a clean,dry 500 mL Pyrex glass graduated mixing cylinder was charged 50 g oftest formulation. Deionized water (50 g) was then slowly and carefullypoured down the side of the flask, with care taken to avoid mixing withthe test formulation, so as to form a separate layer of water on top ofthe test formulation. The cylinder was fitted with a stopper securedwith Parafilm and mounted in the Vertical Rotator Assembly of a GaumFoam Machine (Gaum Inc., Robbinsville, N.J.). The cylinder was rotatedat cycle speed #30 for a total of 20 cycles. The foam volume wasrecorded at two cycle intervals by stopping rotation and reading thefoam volume on the graduated cylinder. The height of the foam wasmeasured at the level where the foam bubbles are dense enough to renderthe graduated cylinder opaque. The Formulation Flash Foam Value wasreported as the average of two individual runs. The Foam GenerationRate, FGR, was calculated by plotting Formulation Flash Foam Value as afunction of shake cycle (2 cycles to 20 cycles) and fitting the data toa straight line function. The FGR is the slope of the resulting linearfit.

Examples E1-E6 and Comparative Examples C1-C3 Preparation of PolymerizedSurfactants

The following polymerized surfactants, Inventive Examples E1-E6 andComparative Examples C1-3 were prepared.

TABLE 1 total avg # #RU mol % ARU avg # Example Description (“DP” ARU(a) SRU (s) C1 hydrolyzed PA-18 50 100 50 0 (Octadecene/MA Copolymer) C2hydrolyzed PA-14 50 100 50 0 (Tetradecene/MA Copolymer) C3 Natrosol Plus1204 1.0 12.0 1192 CS 330 (Cetyl Hydroxyethylcellulose) E1 SodiumTapioca Dextrin 39 7.7 3.0 36 Dodecenylsuccinate E2 Sodium TapiocaDextrin 35 6.3 2.2 33 Dodecenylsuccinate E3 Sodium Tapioca Dextrin 375.8 2.1 35 Dodecenylsuccinate E4 Sodium Potato Dextrin 43 3.3 1.4 42Dodecenylsuccinate E5 Sodium Potato Dextrin 33 3.0 1.0 32Dodecenylsuccinate E6 Sodium Potato Dextrin 33 5.0 1.7 31Dodecenylsuccinate

The polymerized surfactants noted in Table 1 were prepared as follows:PA-18, hydrolyzed, of Comparative Example C1 was obtained by performinga reaction of a 1:1 alternating copolymer of 1-octadecene and maleicanhydride (PA-18 Low Viscosity Low Color grade, commercially availablefrom Chevron Phillips Chemical, LLC) with sodium hydroxide in aqueoussolution to yield a octadecene/MA copolymer having an average of about50 amphiphilic repeat units on a weight average basis, a mole fractionof amphiphilic repeat units of about 100%, and a hydrophobic group ofC16 within the amphiphilic repeat unit.

PA-14, hydrolyzed, of Comparative Example C2 was obtained by performinga reaction of a 1:1 alternating copolymer of 1-tetradecene and maleicanhydride (PA-14) with sodium hydroxide in aqueous solution to yield atetradecene/MA copolymer having a weight average of about 50 amphiphilicrepeat units, a mole fraction of amphiphilic repeat units of about 100%,and a hydrophobic group of C12 within the amphiphilic repeat unit.

Cetyl Hydroxyethylcellulose of Comparative Example 3 was obtained fromHercules, Inc. of Wilmington, Del. as NATROSOL Plus CS 330.

Sodium Tapioca Dextrin Dodecenylsuccinate, of Inventive Examples E1-E3was prepared by the process describe below.

A flask equipped with a stirrer, pH probe, and inlet port was chargedwith 250 g water. To the flask was added a low molecular weight, drytapioca starch dextrin (125 g) and the pH was adjusted to pH 2 with acid(hydrochloric acid:water in a 3:1 mixture). The reaction mixture wasthen charged with the reactive anhydride (dodecenylsuccinic anhydride,12.5 g) and mixed at high speed for one minute. The reaction vessel wasthen placed in a 40° C. constant temperature bath for the remainingreaction time. The pH of the mixture was adjusted to 8.5 using anaqueous sodium hydroxide solution and held constant at 8.5 for 21 hours.After this time, the reaction was cooled and the pH was adjusted to 7using acid (hydrochloric acid:water in a 3:1 mixture).

The Sodium Potato Dextrin Dodecenylsuccinates of Inventive ExamplesE4-E6 was prepared by a similar process as described above for theSodium Tapioca Dextrin Dodecenylsuccinate, except that the flask wascharged with 600 g water, 300 g of a low molecular weight potato starchwas added, the reaction mixture was charged with 23 grams ofdodecenylsuccinic anhydride. Characterization of ARU, SRU and DP forthese inventive examples is shown in Table 1 above.

A representative chemical structure of the inventive sodium dextrindodecenylsuccinates is shown above in the specification under Subclass(B) of representative SACs.

Comparison of Polymerized Surfactants: The polymerized surfactantsprepared in accordance with Examples C1-C3 and E1-E6 were tested fordynamic surface tension reduction in accordance with the above DSA Test.The results of these tests are listed below in Table 2:

TABLE 2 Example Description t_(γ=55) C1 hydrolyzed PA-18 (Octadecene/MACopolymer) >120 C2 hydrolyzed PA-14 (Tetradecene/MA Copolymer) >120 C3Natrosol Plus CS 330 (Cetyl Hydroxyethylcellulose) >120 E1 SodiumTapioca Dextrin Dodecenylsuccinate 35.3 E2 Sodium Tapioca DextrinDodecenylsuccinate 3.7 E3 Sodium Tapioca Dextrin Dodecenylsuccinate <1.0E4 Sodium Potato Dextrin Dodecenylsuccinate 43.0 E5 Sodium PotatoDextrin Dodecenylsuccinate 12.7 E6 Sodium Potato DextrinDodecenylsuccinate 25.2

As seen in Table 2, the Dynamic Surface Tension Reduction, specifically,t_(γ=55), associated with the comparative examples, C1-C3 is greaterthan 120 seconds. The t_(γ=55) for the inventive examples, E1-E6 is lessthan one quarter of those of the comparative examples, indicating theSACs useful in the present invention are capable of providing rapidlydeveloping foam.

Comparison of Polymerized Surfactants: The polymerized surfactantsprepared in accordance with Examples C1-C3 and E1-E6 were tested forsolution viscosity in accordance with the above Solution Viscosity Test.The results of these tests are listed below in Table 3:

TABLE 3 Solution viscosity Example Description (cP) C1 hydrolyzed PA-18(Octadecene/MA Copolymer) 0.85 C2 hydrolyzed PA-14 (Tetradecene/MACopolymer) 0.84 C3 Natrosol Plus CS 330 8227 (CetylHydroxyethylcellulose) E1 Sodium Tapioca Dextrin Dodecenylsuccinate 0.91E2 Sodium Tapioca Dextrin Dodecenylsuccinate 0.91 E3 Sodium TapiocaDextrin Dodecenylsuccinate 0.90 E4 Sodium Potato DextrinDodecenylsuccinate 0.95 E5 Sodium Potato Dextrin Dodecenylsuccinate 0.94E6 Sodium Potato Dextrin Dodecenylsuccinate 0.92

As seen in Table 3, the Solution Viscosity, associated with theInventive examples, E1-E6 is for all of the examples tested, below 1 cP.The polymerized surfactant of Comparative example C3, however, causes adramatic increase in solution viscosity, which can result inunsuitability for foaming cleansers.

Comparison of Polymerized Surfactants: The polymerized surfactantsprepared in accordance with Examples C1-C3 and E1-E6 were tested forfoam in accordance with the above Polymer Foam Test. The results ofthese tests are listed below in Table 4:

TABLE 4 Max Foam Volume Example Description (mL) C1 hydrolyzed PA-18(Octadecene/MA Copolymer) 87 C2 hydrolyzed PA-14 (Tetradecene/MACopolymer) 59 C3 Natrosol Plus CS 330 402 (Cetyl Hydroxyethylcellulose)E1 Sodium Tapioca Dextrin Dodecenylsuccinate 718 E2 Sodium TapiocaDextrin Dodecenylsuccinate 745 E3 Sodium Tapioca DextrinDodecenylsuccinate 734 E4 Sodium Potato Dextrin Dodecenylsuccinate 469E5 Sodium Potato Dextrin Dodecenylsuccinate 452 E6 Sodium Potato DextrinDodecenylsuccinate 773

As seen in Table 4, the Foam Volume as determined by the Polymer FoamTest, for Inventive examples, E1-E6 is greater than 100 mL, whereasComparative examples C1 and C2 is considerably lower. It can also beseen that the compositions that include SACs are also capable ofproviding a high level of foam, despite the absence of monomericsurfactant. The foam volume shown by C1 and C2 can, in use, result inthe need to add additional foaming agents in order to meet the foamingrequirements of the end user. This can cause an undesirable increase inraw material costs.

Examples E7-E12 and Comparative Examples C4-C5 Preparation of ModelCompositions for Dynamic Light Scattering Test

Model compositions of Inventive Examples E7 through E12 as well asComparative Examples C4 and C5 were prepared in order to perform the DLStest. The model compositions were prepared by separately blending theparticular polymerized surfactants shown above with other ingredients asfollows: Water (about 50.0 parts) was added to a beaker fitted with amechanical stirrer and hotplate. Sodium Methylparaben (and) SodiumPropylparaben (and) Sodium Ethylparaben (Nipasept Sodium, ClariantCorp.) powder was added and mixed until dissolved. The polymerizedsurfactant was then added at low stir speed, to avoid aeration.Tetrasodium EDTA (Versene XL, Dow Chemical) was added and mixing wascontinued. Heat was provided (no greater than 60° C.) if necessary toobtain a uniform solution. The batch was allowed to cool to 25° C. ifnecessary, while mixing was continued at medium speed. pH was adjustedto 7.0±0.2 using citric acid or sodium hydroxide solution. Water wasadded to q.s. to 100%. The model compositions are shown in Table 5,below:

TABLE 5 Polymerized Surfactant INCI Name C4 C5 E7 E8 E9 E10 E11 E12 C1Octadecene/MA 18.46  — — — — — — — Copolymer C2 Tetradecene/MA — 18.46 — — — — — — Copolymer E1 Sodium Tapioca — — 5.05 — — — — — DextrinDodecenylsuccinate (prop.) E2 Sodium Tapioca — — — 5.05 — — — — DextrinDodecenylsuccinate (prop.) E3 Sodium Tapioca — — — — 5.05 — — — DextrinDodecenylsuccinate (prop.) E4 Sodium Potato — — — — — 5.05 — — DextrinDodecenylsuccinate (prop.) E5 Sodium Potato — — — — — — 5.05 — DextrinDodecenylsuccinate (prop.) E6 Sodium Potato — — — — — — — 5.05 DextrinDodecenylsuccinate (prop.) Nipasept Sodium 0.30 0.30 0.30 0.30 0.30 0.300.30 0.30 Sodium Methylparaben (and) Sodium Propylparaben (and) SodiumEthylparaben Versene Tetrasodium EDTA 0.25 0.25 0.25 0.25 0.25 0.25 0.250.25 100XL (50%) Sodium Sodium Hydroxide q.s. q.s. q.s. q.s. q.s. q.s.q.s. q.s. Hydroxide solution (20%) Citric Acid Citric Acid q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s. solution (20%) Purified Water q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s. WaterComparison of Model Compositions: The model compositions prepared inaccordance with Examples C1-C3 and E1-E6 were tested for dynamic lightscattering in accordance with the above DLS Test. The results of thesetests are listed below in Table 6:

TABLE 6 Z-Average Micelle Fraction of d_(H) (nm), micelles with PMODd_(H) < 9 nm, Example Description z-average PMOD % C4 hydrolyzed PA-18(Octadecene/ 15.1 10.0 MA Copolymer) C5 hydrolyzed PA-14 (Tetradecene/48.6 4.0 MA Copolymer) C6 Natrosol Plus CS 330 (Cetyl — —Hydroxyethylcellulose) E7 Sodium Tapioca Dextrin 6.51 69.8Dodecenylsuccinate E8 Sodium Tapioca Dextrin 16.9 30.1Dodecenylsuccinate E9 Sodium Tapioca Dextrin — — Dodecenylsuccinate  E10Sodium Potato Dextrin 12.7 29.1 Dodecenylsuccinate  E11 Sodium PotatoDextrin 30.1 11.5 Dodecenylsuccinate  E12 Sodium Potato Dextrin 8.9242.3 Dodecenylsuccinate

Table 6 indicates that the Inventive examples, E1-E6 provide a fractionof small micelles (as indicated by PMOD %) that is surprisingly low,i.e., <90%. This is suggestive that the inventive examples willdesirably provide low irritation.

Inventive Examples E13-E16 and Comparative Examples C7-C8 Preparation ofInventive and Comparative Examples

Preparation of Inventive Examples E13-E16: Liquid cleanser formulations(shown in Table 7 below) were prepared as follows: To a beaker fittedwith a mechanical stirrer and hotplate were added water (about 40.0parts) and Glycerin. Mixing at low-medium speed and heating to 75° C.were commenced. The example SAC polymer was then added. (Note: In thecase of Comparative Example polymers C1 and C2, 11.25 parts of 20%Sodium Hydroxide solution were added to facilitate hydrolysis in situ.)As the batch reached 60° C., PEG-120 Methyl Glucose Dioleate was added.The batch was allowed to mix at 75° C. until all solids were dissolvedand the batch was uniform. Heating was then stopped and the batchallowed to cool to ca. 50° C., at which point Cocamidopropyl Betaine wasadded. Upon cooling to below 40° C., Tetrasodium EDTA, DMDM Hydantoin,and Fragrance were added. In a separate vessel, Polyquaternium-10 andWater (15.0 parts) were combined and mixed until completely dissolved;this mixture was then added to the main batch. The batch was allowed tocool to 25° C. if necessary, while mixing was continued at medium speed.pH was adjusted to 7.0±0.2 using citric acid or sodium hydroxidesolution. Water was added to q.s. to 100%.

In the case of Comparative Examples C7 and C8, a modified procedure wasemployed as follows: To a beaker fitted with a mechanical stirrer andhotplate was added water (about 40.0 parts) Mixing at low-medium speedand heating to 90° C. were commenced. The comparative example polymerwas then added. To facilitate in situ hydrolysis, 11.25 parts of 20%Sodium Hydroxide solution was added, and the batch mixed at 90° C. untilthe polymer was completely dissolved, at which point heating wasstopped. Upon cooling to 75° C., PEG-120 Methyl Glucose Dioleate wasadded. The batch was allowed to mix at 75° C. until all solids weredissolved and the batch was uniform. Heating was then stopped and thebatch allowed to cool to ca. 50° C., at which point CocamidopropylBetaine was added. Upon cooling to below 40° C., Tetrasodium EDTA, DMDMHydantoin, and Fragrance were added. In a separate vessel,Polyquaternium-10 and Water (15.0 parts) were combined and mixed untilcompletely dissolved; this mixture was then added to the main batch. Thebatch was allowed to cool to 25° C. if necessary, while mixing wascontinued at medium speed. pH was adjusted to 7.0±0.2 using citric acidor sodium hydroxide solution. Water was added to q.s. to 100%.

TABLE 7 Polymerized Surfactant INCI Name C7 C8 E13 E14 E15 E16 C1Octadecene/MA 9.00 — — — — — Copolymer C2 Tetradecene/MA — 9.00 — — — —Copolymer E2 Sodium Tapioca — — 9.00 — — — Dextrin Dodecenylsuccinate(prop.) E4 Sodium Potato Dextrin — — — 9.00 — — Dodecenylsuccinate(prop.) E5 Sodium Potato Dextrin — — — — 9.00 — Dodecenylsuccinate(prop.) E6 Sodium Potato Dextrin — — — — — 9.00 Dodecenylsuccinate(prop.) Tegobetaine L7-V Cocamidopropyl 7.00 7.00 7.00 7.00 7.00 7.00(30%) Betaine Emery 917 Glycerin 5.00 5.00 5.00 5.00 5.00 5.00 GlucamateDOE- PEG-120 Methyl 7.00 7.00 7.00 7.00 7.00 7.00 120 Glucose DioleateVersene 100XL Tetrasodium EDTA 1.00 1.00 1.00 1.00 1.00 1.00 (50%)Glydant (55%) DMDM Hydantoin 0.50 0.50 0.50 0.50 0.50 0.50 Polymer JR400Polyquaternium-10 0.15 0.15 0.15 0.15 0.15 0.15 Fragrance Fragrance 0.200.20 0.20 0.20 0.20 0.20 Sodium Hydroxide Sodium Hydroxide q.s. q.s.q.s. q.s. q.s. q.s. solution (20%) Citric Acid solution Citric Acid q.s.q.s. q.s. q.s. q.s. q.s. (20%) Purified Water Water q.s. q.s. q.s. q.s.q.s. q.s.Comparison of Compositions: The compositions prepared in accordance withExamples C₇-C₈ and E13-E16 were tested for foam in accordance with theabove Formulation Foam Test. The results of these tests are listed belowin Table 8:

TABLE 8 Max Foam Volume Example (mL) C7  78 C8  73 E13 267 E14 246 E15227 E16 267

As seen in Table 8, the foam associated with the Inventive examples,E13-E16 is considerably higher (about triple) than those measured forcomparative examples C7 and C8.

Inventive Examples E17-E20 Preparation and Testing of Inventive Examples

The QUAB® 342 (quat reagent) modified potato dextrin polymers of E17-E20were prepared by charging a flask equipped with a stirrer, pH probe, andinlet port with 600 g water. To the flask dry potato starch dextrin (300g) was added. Also, 2.4 grams of sodium hydroxide was added as a 3%aqueous solution (80 mLs) at the rate of 7.5 mls/minute. The reactionwas then heated to 43° C. and allowed to stir for 30 minutes attemperature. Approximately ½ the total amount of sodium hydroxide neededto neutralize the quat reagent was added at 7.5 mls/minute. The totalactive charge of QUAB® 342 quat reagent (30 grams for E17, 6 grams forE18, 60 grams for E19, and 90 grams for E20) was added by pouring thereagent into the reaction vessel with agitation. The remainder of thesodium hydroxide was then added at 7.5 mls/minutes until the pH of thereaction was at or slightly above 11.5. The reaction was stirredovernight at 43° C. (approximately 18 hours) and then cooled to roomtemperature (25° C.). The pH was adjusted to 5.5 using dilute (10%)hydrochloric acid and the product was recovered by precipitating intoisopropyl alcohol. The powder was washed three times with 500 mls ofisopropyl alcohol and then air dried. The total bound nitrogen forE17-E20 was 0.28% for E17, 0.10% for E18, 0.38% for E19, and 0.53% forE20.

TABLE 9 avg # avg # total #RU mol % ARU SRU Example Description (“DP”ARU (a) (s) E17 Laurdimonium 33 3.4 1.1 32 Hydroxypropyl Potato DextrinChloride E18 Laurdimonium 33 1.2 0.4 33 Hydroxypropyl Potato DextrinChloride E19 Laurdimonium 33 4.8 1.6 31 Hydroxypropyl Potato DextrinChloride E20 Laurdimonium 33 6.9 2.3 31 Hydroxypropyl Potato DextrinChloride

The polymerized surfactants prepared in accordance with Examples E17-E20were tested for dynamic surface tension reduction in accordance with theabove DSA Test. The results of these tests are listed below in Table 10:

TABLE 10 Example Description t_(γ=55) E17 Laurdimonium HydroxypropylPotato Dextrin Chloride >120 E18 Laurdimonium Hydroxypropyl PotatoDextrin Chloride >120 E19 Laurdimonium Hydroxypropyl Potato DextrinChloride >120 E20 Laurdimonium Hydroxypropyl Potato Dextrin Chloride>120The polymerized surfactants prepared in accordance with Examples E17-E20were tested for foam in accordance with the above Polymer Foam Test. Theresults of these tests are listed below in Table 11:

TABLE 11 Max Foam Example Description Volume (mL) E17 LaurdimoniumHydroxypropyl Potato 369 Dextrin Chloride E18 Laurdimonium HydroxypropylPotato 30 Dextrin Chloride E19 Laurdimonium Hydroxypropyl Potato 542Dextrin Chloride E20 Laurdimonium Hydroxypropyl Potato 758 DextrinChloride

Compositions E21-E24 and DLS Testing Thereof:

Model compositions of Inventive Examples E21-E24 were prepared in orderto perform the DLS test. The model compositions were prepared byseparately blending the particular polymerized surfactants shown abovewith other ingredients as follows: Water (about 50.0 parts) was added toa beaker fitted with a mechanical stirrer and hotplate. SodiumMethylparaben (and) Sodium Propylparaben (and) Sodium Ethylparaben(Nipasept Sodium, Clariant Corp.) powder was added and mixed untildissolved. The polymerized surfactant was then added at low stir speed,to avoid aeration. Tetrasodium EDTA (Versene XL, Dow Chemical) was addedand mixing was continued. Heat was provided (no greater than 60° C.) ifnecessary to obtain a uniform solution. The batch was allowed to cool to25° C. if necessary, while mixing was continued at medium speed. pH wasadjusted to 7.0±0.2 using citric acid or sodium hydroxide solution.Water was added to q.s. to 100%. The model compositions are shown inTable 12, below:

TABLE 12 Polymerized Surfactant INCI Name E21 E22 E23 E24 E17Laurdimonium 5.05 — — — Hydroxypropyl Potato Dextrin Chloride (prop.)E18 Laurdimonium — 5.05 — — Hydroxypropyl Potato Dextrin Chloride(prop.) E19 Laurdimonium — — 5.05 — Hydroxypropyl Potato DextrinChloride (prop.) E20 Laurdimonium — — — 5.05 Hydroxypropyl PotatoDextrin Chloride (prop.) Niapsept Sodium Sodium Methyl 0.30 0.30 0.300.30 Paraben (and) Sodium Propylparaben (and) Sodium EthylparabenVersene 100XL (50%) Tetrasodium EDTA 0.25 0.25 0.25 0.25 SodiumHydroxide Sodium Hydroxide q.s. q.s. q.s. q.s. soluton (20%) Citric Acidsolution Citric Acid q.s. q.s. q.s. q.s. (20%) Purified Water Water q.s.q.s. q.s. q.s.

The model compositions prepared in accordance with Examples E21-E24 weretested for dynamic light scattering in accordance with the above DLSTest. The results of these tests are listed below in Table 13:

TABLE 13 Fraction Z-Average of Micelle micelles d_(H) (nm), with d_(H) <PMOD z- 9 nm, Example Description average PMOD % E21 LaurdimoniumHydroxypropyl Potato 11.5 32.1 Dextrin Chloride E22 LaurdimoniumHydroxypropyl Potato 12.0 36.1 Dextrin Chloride E23 LaurdimoniumHydroxypropyl Potato 11.1 31.5 Dextrin Chloride E24 LaurdimoniumHydroxypropyl Potato 10.1 36.4 Dextrin Chloride

Examples E25-E32 Preparation of Inventive Personal Care Compositions andMeasurement of Formulation Viscosity

The following personal care compositions, Inventive Examples E25-E32,and were prepared and tested for Formulation Viscosity. Each ofInventive Examples E25-E32 included a SAC and a corona thickener.

TABLE 14 Tradename INCI Name E25 E26 E27 E28 E29 E30 E31 E32 HM StarchSodium Dextrin 31.64  31.64  31.64  31.64  31.64  31.64  31.64  31.64 Slurry (29%) Dodecenylsuccinate (prop.) Tegobetaine Cocamidopropyl 7.007.00 7.00 7.00 7.00 7.00 7.00 7.00 L7-V (30%) Betaine Emery 917 Glycerin5.00 5.00 5.00 1.75 5.00 5.00 5.00 5.00 Ethox PEG PEG-150 1.40 1.60 — —— — — — 6000 DS Distearate Special Glucamate PEG-120 Methyl — — 6.10 — —— — — DOE-120 Glucose Dioleate Glucamate PEG-120 Methyl — — — 10.0  — —— — LT Glucose Trioleate (and) Propylene Glycol (and) Water Ethox HVBPEG-175 — — — — 1.75 — — — Diisostearate Ethox NED-2 Decyltetradeceth- —— — — — 1.40 — — 200 Dimerate Ethox Decyltetradeceth- — — — — — — 1.28 —NEBS-2 200 Behenate Ethox PEG PEG-150 — — — — — — — 1.85 6000 DBDibehenate Versene Tetrasodium 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00100XL EDTA (50%) Glydant DMDM 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50(55%) Hydantoin Fragrance Fragrance 0.20 0.20 0.20 0.20 0.20 0.20 0.200.20 Sodium Sodium q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. HydroxideHydroxide solution (20%) Citric Acid Citric Acid q.s. q.s. q.s. q.s.q.s. q.s. q.s. q.s. solution (20%) Purified Water q.s. q.s. q.s. q.s.q.s. q.s. q.s. q.s. Water Viscosity (cP) 226.5   1734     3427    2930     2090     1015     2380     4190    

Sodium Tapioca Dextrin Dodecenylsuccinate, of Inventive Examples E25-E32was prepared by the process describe below.

A flask equipped with a stirrer, pH probe, and inlet port was chargedwith 250 g water. To the flask was added a low molecular weight, drytapioca starch dextrin (125 g) and the pH was adjusted to pH 2 with acid(hydrochloric acid:water in a 3:1 mixture). The reaction mixture wasthen charged with the reactive anhydride (dodecenylsuccinic anhydride,12.5 g) and mixed at high speed for one minute. The reaction vessel wasthen placed in a 40° C. constant temperature bath for the remainingreaction time. The pH of the mixture was adjusted to 8.5 using anaqueous sodium hydroxide solution and held constant at 8.5 for 21 hours.After this time, the reaction was cooled and the pH was adjusted to 7using acid (hydrochloric acid:water in a 3:1 mixture).

Inventive Example, Ex. 25 was prepared as follows: to an appropriatelysized vessel equipped with a hotplate and overhead mechanical stirrer,60 parts Water was added. While mixing at 200-250 rpm and heating to85-90° C., Glycerin and Sodium Dextrin Dodecenylsuccinate slurry wereadded. At 65° C., PEG-150 Distearate was added. The batch was mixed at85-90° C. until all PEG-150 Distearate was dissolved. Upon completedissolution of all PEG-150 Distearate, heating was stopped and the batchwas allowed to cool to 50° C. while mixing at 200-250 rpm. At 50° C.,Cocamidopropyl Betaine was added to the batch, and the batch was allowedto cool below 40° C., at which point Tetrasodium EDTA, DMDM Hydantoin,and Fragrance were added. The batch was allowed to mix while cooling tobelow 30° C. and was then adjusted to pH 6.7-7.2 (target pH=6.9) usingnecessary amounts of Citric Acid and/or Sodium Hydroxide. Water wasadded in q.s. to 100 wt %, and the batch was allowed to mix untiluniform before being discharged to an appropriate storage vessel.Inventive Examples Ex. 26-Ex. 32 were prepared in a similar manner.Formulation Viscosity was measured for each of the Inventive Examplesusing the Formulation Viscosity Test described above. FormulationViscosity (in centipoise, cP) is reported in Table 14.

As is apparent from Table 14, a variety of micellar thickeners can becombined with Sodium Dextrin Dodecenylsuccinate (a SAC) to achieveviscosities that vary from, for example as low as 226 cP to as high as4190 cP.

Characterization of the SAC of E13-E28 and C7 (HM Slurry) shows that ithas total of 37 RUs with a mol % ARU of 6.1, which breaks down to anaverage of 2.3 ARUs (a) and 35 SRUs (s). The t_(γ=55) for this sample isgreater than 120 seconds. The solution viscosity for the sample is <2 cP(estimated according to DP). The maximum foam volume for the sample is195 mL. When made using the procedures in the Preparation of ModelCompositions for Dynamic Light Scattering Test, the Z-Average Micelled_(H) is 15.2 nm and the fraction of micelles with d_(H) is 34.7%.

Examples E33-E36 Preparation of Inventive Personal Care Compositions andMeasurement of Formulation Viscosity

The following personal care compositions, Inventive Examples E-E36 andwere prepared and tested for Formulation Viscosity.

TABLE 8 Tradename INCI Name E33 E34 E35 E36 HM Starch Slurry (29%)Sodium Dextrin 31.64  31.64  31.64  31.64  Dodecenylsuccinate (prop.)Tegobetaine L7-V Cocamidopropyl Betaine 7.00 7.00 7.00 7.00 (30%) Emery917 Glycerin 5.00 5.00 5.00 5.00 Glucamate DOE-120 PEG-120 MethylGlucose 3.00 6.10 7.00 8.50 Dioleate Versene 100XL (50%) TetrasodiumEDTA 1.00 1.00 1.00 1.00 Glydant (55%) DMDM Hydantoin 0.50 0.50 0.500.50 Fragrance Fragrance 0.20 0.20 0.20 0.20 Sodium Hydroxide SodiumHydroxide q.s. q.s. q.s. q.s. solution (20%) Citric Acid solution CitricAcid q.s. q.s. q.s. q.s. (20%) Purified Water Water q.s. q.s. q.s. q.s.Viscosity (cP) 36.9  3427     3712     8325    

Inventive Examples, Ex. 33-Ex. 36 were prepared in a manner similarly toInventive Examples Ex. 13-Ex. 20. As is apparent from Table 14, byincreasing the concentration of PEG-120 Methyl Glucose Dioleate, one isable to increase the viscosity of a composition that includes SodiumDextrin Dodecenylsuccinate from, for example, about 37 cP to about 8325cP.

Examples E37-E40 Preparation of Inventive Personal Care Compositions andMeasurement of Formulation Viscosity

The following personal care compositions, Inventive Examples E37-E40 andwere prepared and tested for Formulation Viscosity.

TABLE 15 Tradename INCI Name E37 E38 E39 E40 HM Starch Slurry SodiumDextrin 31.64  31.64  31.64  31.64  (29%) Dodecenylsuccinate (prop.)Tegobetaine L7-V Cocamidopropyl Betaine 7.00 7.00 7.00 7.00 (30%) Emery917 Glycerin 5.00 5.00 5.00 5.00 Ethox PEG 6000 PEG-150 Distearate 1.401.60 1.80 1.90 DS Special Versene 100XL Tetrasodium EDTA 1.00 1.00 1.001.00 (50%) Glydant (55%) DMDM Hydantoin 0.50 0.50 0.50 0.50 FragranceFragrance 0.20 0.20 0.20 0.20 Sodium Hydroxide Sodium Hydroxide q.s.q.s. q.s. q.s. solution (20%) Citric Acid solution Citric Acid q.s. q.s.q.s. q.s. (20%) Purified Water Water q.s. q.s. q.s. q.s. Viscosity (cP)226.5   1734     2892     4245    

Inventive Examples, Ex. 37-Ex. 40 were prepared in a manner similarly toInventive Examples Ex. 33-Ex. 36, but using a different micellarthickener. As is apparent from Table 15, by increasing the concentrationof PEG-150 Distearate, one is also able to increase the viscosity of thecomposition that includes Sodium Dextrin Dodecenylsuccinate from, forexample, about 226 cP to about 4245 cP. Similarly to Inventive ExamplesEx. 33-Ex. 36, the increase in Formulation Viscosity is highlynon-linear with respect to concentration of micellar thickener.

Comparative Example C8 Preparation of Comparative Personal CareCompositions and Measurement of Formulation Viscosity

The following personal care composition, Comparative Example C8 wasprepared and tested for Formulation Viscosity.

TABLE 16 Tradename INCI Name C8 HM Starch Slurry Sodium StarchDodecenylsuccinate (prop.) 31.64 (29%) Tegobetaine L7-V CocamidopropylBetaine 7.00 (30%) Emery 917 Glycerin 5.00 Carbopol AQUA AcrylatesCopolymer 7.00 SF-1 (30%) Versene 100XL Tetrasodium EDTA 1.00 (50%)Glydant (55%) DMDM Hydantoin 0.50 Fragrance Fragrance 0.20 SodiumHydroxide Sodium Hydroxide q.s. solution (20%) Citric Acid solutionCitric Acid q.s. (20%) Purified Water Water q.s. Viscosity (cP) 4875

Comparative Example, C8 was prepared in a similar manner to the previousInventive Example, Ex. 35, except that Carbopol Aqua SF-1 (aconventional, high molecular weight, “alkali-swellable emulsionpolymeric thickener”) was substituted for PEG-120 Methyl GlucoseDioleate. The Formulation Viscosity was measured to be 4875 cP(reasonably close to Inventive Example, Ex. 35).

Comparison of Formulation Flash Foam Values for Personal CareCompositions

Inventive Example, Ex. 35 and Comparative Example C8 were tested forFormulation Flash Foam Value using the Formulation Flash Foam Testdescribed above. The data is shown in Table 17 below. The two data sets(one for Comparative Example C8 and the other for Inventive Example, Ex.35) are also shown in FIG. 1.

TABLE 17 Foam Volume of C7 (mL) Foam Volume of E23 (mL) Std Run StdCycles Run 1 Run 2 Avg Dev Run 1 2 Avg Dev 2 145 125 135 14 130 135 1334 4 165 150 158 11 160 160 160 0 6 200 175 188 18 200 240 220 28 8 225200 213 18 250 250 250 0 10 225 225 225 0 300 300 300 0 12 250 240 245 7350 350 350 0 14 250 250 250 0 400 400 400 0 16 270 260 265 7 450 450450 0 18 280 265 273 11 500 500 500 0 20 290 275 283 11 525 520 523 4

As can be readily seen in Table 17, Inventive Example, Ex. 35essentially develops greater flash foam, e.g., a higher amount of foamthan Comparative Example, C8, when compared at most points (number ofcycles) during the test. Inventive Example, Ex. 35 also reaches aterminal foam volume at 20 cycles that is 84% higher than that ofComparative Example, C8 (523 compared with 283).

Furthermore, as can be seen in FIG. 1, the Foam Generation Rate, FGR,for Inventive Example, Ex. 35 is almost triple that of ComparativeExample, C8 (22.84 compared with 8.04). Applicants attribute thissuperiority in performance of the Inventive Examples to the dramaticimprovement in the micellar thickener-thickened formula to “break” andlose viscosity upon dilution. By comparison, the SAC-containingcompositions that are thickened with the conventional high molecularweight alkali-swellable emulsion polymeric thickeners do not readily“break” upon dilution and are relatively poor flash foamers.

The following Examples are included to illustrate the effect molecularweight, differing amounts of hydrophobic reagents and the use ofdifferent starch-based SACs on clarity, viscosity, foam generation andfoam stability as it relates to the present invention.

Example 41 The Preparation of an Aqueous Solution of Native (Unmodified)Tapioca Starch

An aqueous solution of native (unmodified) tapioca was prepared bysuspending 10 g dry native tapioca starch in 200 g water. The mixturewas heated at 80° C. with stirring for 30 minutes. The resulting thickand translucent solution was allowed to cool.

Example 42 The Preparation of an Aqueous Solution of a Tapioca StarchDextrin

An aqueous solution of tapioca starch dextrin was prepared by suspending10 g tapioca dextrin in 100 g water. The suspension was mixed withoutheating until the power dissolved. The resulting solution was slightlyhazy.

Example 43 The Preparation of an Aqueous Solution of a DodecenylsuccinicAnhydride Modified Tapioca Starch Dextrin

An aqueous solution of a dodecenylsuccinic anhydride modified tapiocastarch dextrin was prepared by charging a flask equipped with a stirrer,pH probe, and inlet port with 250 g water. To the flask, dry tapiocastarch dextrin (125 g) was added and the pH was adjusted to a pH of 2with acid (hydrochloric acid:water in a 3:1 mixture). The reactionmixture was then charged with the reactive anhydride (dodecenylsuccinicanhydride, 12.5 g) and mixed at high speed for one minute. The reactionvessel was then placed in a 40° C. constant temperature bath for theremaining reaction time. The pH of the mixture was adjusted to 8.5 usingan aqueous sodium hydroxide solution and held constant at 8.5 for 21hours. After this time, the reaction was cooled and the pH adjusted to 7using acid (hydrochloric acid:water in a 3:1 mixture). It should benoted that the starch solution prepared according to this example caneither be used immediately or stored for future use. If it is stored, itmust be refrigerated, preserved, or spray dried.

Example 44 The Preparation of an Aqueous Solution of a OctenylsuccinicAnhydride (OSA) Modified Potato Starch Dextrin

An aqueous solution of octenylsuccinic anhydride (OSA) was prepared bycharging a flask equipped with a stirrer, pH probe, and inlet port with600 g water. To the flask dry tapioca starch dextrin (300 g) was addedand the pH was adjusted to a pH of 2 with acid (hydrochloric acid:waterin a 3:1 mixture). The reaction mixture was then charged with thereactive anhydride (octenylsuccinic anhydride, 23 g) and mixed at highspeed for one minute. The reaction vessel was then placed in a 40° C.constant temperature bath for the remaining reaction time. The pH of themixture was adjusted to 8.5 using an aqueous sodium hydroxide solutionand held constant at 8.5 for 21 hours. After this time, the pH wasadjusted to 7 using acid (hydrochloric acid:water in a 3:1 mixture). Itshould be noted that the starch solution prepared according to thisexample can either be used immediately or stored for future use. If itis stored, it must be refrigerated, preserved, or spray dried.

Example 45 Preparation of QUAB® 342 Modified Potato Dextrin Samples

A QUAB® 342 modified potato dextrin was prepared by charging a flaskequipped with a stirrer, pH probe, and inlet port with 600 g water. Tothe flask dry potato starch dextrin (300 g) was added. Also, 2.4 gramsof sodium hydroxide was added as a 3% aqueous solution (80 mLs) at therate of 7.5 mls/minute. The reaction was then heated to 43° C. andallowed to stir for 30 minutes at temperature. Approximately ½ the totalamount of sodium hydroxide needed to neutralize the quat reagent wasadded at 7.5 mls/minute. The total charge of quat (30 grams activereagent, 10% by weight active reagent based on starch) was added bypouring the reagent into the reaction vessel with agitation. Theremainder of the sodium hydroxide was then added at 7.5 mls/minutesuntil the pH of the reaction was at or slightly above 11.5. The reactionwas stirred overnight at 43° C. (approximately 18 hours) and then cooledto room temperature (25° C.). The pH was adjusted to 5.5 using dilute(10%) hydrochloric acid and the product was recovered by precipitatinginto isopropyl alcohol. The powder was washed three times with 500 mlsof isopropyl alcohol and then air dried. The bound nitrogen was found tobe 0.28 percent, as reported for Sample 13. Samples 14 and 15 wereprepared according to the procedure above, except that the amount ofactive quat charged to the reaction was 20% and 30%, respectively.

Example 46 Clarity in Water

Sample 1 was prepared according to Example 41. Sample 2 was preparedaccording to Example 42. Samples 3-5 and 10 were prepared as in Example43 using degraded tapioca starches with noted molecular weights. Samples6 and 8 were prepared as in Example 43 using differing amounts of DDSA.Sample 7 was prepared as in Example 43 using a potato base and increasedDDSA. Sample 9 was prepared as in Example 43 using a corn base. Sample11 was prepared as in Example 43 using a potato base. Sample 12 wasprepared according to Example 44. Sample 13, 14 and 15 were preparedusing the process of Example 45.

The samples were tested as a 10% solids solution in water. The solutionwas evaluated visually as opaque (FAIL) or translucent or clear (PASS).The passing samples were then evaluated at 10% solids using a turbiditytest (model 2100N Hach laboratory turbidimeter) and the sample claritycategorized as excellent (<=10 ntu), slightly hazy (greater than 10 to120 ntu inclusive), hazy (greater than 120 ntu to 400 ntu inclusive), orfailing (greater than 400 ntu). The results of the test are shown inTable 18.

TABLE 18 Hydrophobe Mw of Clarity Sample level polysaccharide evaluationntu 1 0 >1,000,000 Fail Opaque 1 (5% solution) 0 >1,000,000 sl. Hazy 832 0 6442 sl. Hazy 57 3 5.52 6442 sl. Hazy 102 4 6.4 23170 Hazy 157 5 4.691223 Fail Opaque 6 0.95 6442 Hazy 160 7 10.2 5425 Excellent 5 8 7.796308 sl. Hazy 93 9 1.3 7344 Fail 562 10 5.33 4568 sl. Hazy 78 11 4.585425 Excellent 8 12 7.6 (OSA) 5425 Excellent 5 13 0.28N (QUAB) 5425Excellent 7.43 14 0.38N (QUAB) 5425 Excellent 9.69 15 0.50N (QUAB) 5425sl. Hazy 11.80This Example shows the effect of molecular weight on the clarity ofsolution, with the lower molecular weight corresponding to a clearersolution.

Example 47 SAC Viscosity Test (in Water)

A 10% solids solution of each sample in water was prepared. If thesolution was noticeably thick (>1000 cps) it failed. Only sample 1failed. The other samples were tested for Brookfield viscosity with #3spindle and at 200 rpm. The results are shown in Table 19.

TABLE 19 Hydrophobe Mw of Viscosity Viscosity Sample levelpolysaccharide evaluation (cps) 1 0 >1,000,000 Fail NA 1 (5% solution)0 >1,000,000 Fail 2 0 6442 Pass 5 3 5.52 6442 Pass 5 4 6.4 23170 Pass 55 4.6 91223 Pass 7.5 6 0.95 6442 Pass 5 7 10.2 5425 Pass 5 8 7.79 6308Pass 7 9 1.3 7344 Pass 5 10 5.33 4568 Pass 5 11 4.58 5425 Pass 25 12 3.8(OSA) 5425 Pass 25

Example 48 Foam Generation in Water

A 10% solids solution of each sample in water was prepared. The sampleswere screened for foam generation by adding 5 g of solution into a 20 mlscintillation vial, gently shaking ten times, and measuring the foamgenerated in the headspace above the liquid. If the foam head wasgreater than or equal to 0.75″ the test was noted as PASS, if the foamhead was less than 0.75″ the test was noted as FAIL.

To distinguish between excellent and good foaming performance theFormulation Foam Test described previously was run. For the test, asolution of the polymer was prepared by dissolving the polymer (5 g) inwater (900 g), adding Glydant preservative (3 g) and tetrasodium EDTA (5g), adjusting the pH to 7.0+/−0.2 with sodium hydroxide (20 wt % inwater) and/or citric acid (20 wt. % in water), followed by the additionof water to reach 1000 mL total volume for the test. The test solutionwas then added to the sample tank of a Sita R-2000 foam tester and runaccording to the Formulation Foam Test described previously. TheFormulation Foam reported in this example was the value at 150 seconds.Those samples exceeding 575 mL of foam volume at that time weredesignated as “excellent” foaming samples. The results are set forth inTable 20.

TABLE 20 Hydrophobe Mw of Foam Foam height @ Sample level polysaccharideGeneration 150 seconds 1 0 >1,000,000 Fail 2 0 6442 Fail 3 5.52 6442Pass 450 4 6.4 23170 Pass 550 5 4.6 91223 Pass 500 6 0.95 6442 Fail 710.2 5425 Pass (excellent) 750 8 7.79 6308 Pass (excellent) 600 9 1.37344 NA 10 5.33 4568 Pass 400 11 4.58 5425 Pass 400 12 3.8 (OSA) 5425Fail

Example 49 Foam Stability in Water

A 10% solids solution of each of samples 1-12 in water was prepared. Thesamples were screened for foam generation as described in Example 48 andthen the vials were set aside for four hours. If some foam was stillevident in the vial after that time the foam was noted as persistent andrated as a PASS for the foam stability test.

In order to distinguish between good and excellent foam performance, theSITA foam tester was used as in Example 48. The percent of the foam headremaining 1000 seconds after the stirring was removed was used toquantify the foam stability. Those samples having a retention of between5 and 50 percent were classified as having GOOD foam stability, thosewith a retention 50 percent and greater were classified as havingEXCELLENT foam stability. The results are summarized in Table 21.

TABLE 21 Hydrophobe Mw of Foam Stability Foam retention Sample levelpolysaccharide Screen @ 1000 sec. 1 0 >1,000,000 NA 2 0 6442 NA 3 5.526442 Pass (good) 15% 4 6.4 23170 Pass (good) 40% 5 4.6 91223 Pass (good)40% 6 0.95 6442 NA 7 10.2 5425 Pass (excellent) >90% 8 7.79 6308 Pass(excellent) >80% 9 1.3 7344 NA 10 5.33 4568 Pass (good) 15% 11 4.58 5425Pass (excellent) >80% 12 3.8 (OSA) 5425 NA

While particular embodiments of the present invention have beenillustrated and described herein, the invention is not intended to belimited to the details shown. Rather, various modifications may be madein the details within the range and scope of equivalents of the claimsand without departing from the spirit and scope of the invention.

1. A method of cleansing or treating the human body comprising applyingto the human body a composition comprising a superhydrophilicamphiphilic copolymer, a micellar thickener, and acosmetically-acceptable or pharmaceutically-acceptable carrier.
 2. Themethod of claim 1 wherein said superhydrophilic amphiphilic copolymerhas a DP between 4 and about
 500. 3. The method of claim 1 wherein saidsuperhydrophilic amphiphilic copolymer has a mole percent of amphiphilicunits that is less
 10. 4. The method of claim 1 wherein saidsuperhydrophilic amphiphilic copolymer has a weight average molecularweight that is from about 1000 to about 100,000.
 5. The method of claim1 wherein said superhydrophilic amphiphilic copolymer has a DynamicSurface Tension Reduction, t_(γ=55), of less than about 120 seconds. 6.The method of claim 1 wherein said superhydrophilic amphiphiliccopolymer has a solution viscosity of less than about 9 centipoise. 7.The method of claim 1 wherein said superhydrophilic amphiphiliccopolymer has a PMOD % of less than about 90%.
 8. The method of claim 1wherein said superhydrophilic amphiphilic copolymer comprises aplurality of SRUs derived from ethylenically-unsaturated monomers and atleast one ARU derived from an ethylenically-unsaturated monomer.
 9. Themethod of claim 1 wherein said superhydrophilic amphiphilic copolymercomprises a plurality of monosaccharide SRUs.
 10. The method of claim 1wherein said composition comprises an aqueous carrier.
 11. The method ofclaim 1 wherein said superhydrophilic amphiphilic copolymer comprises astarch-based polysaccharide modified with a hydrophobic reagent having aweight average molecular weight that is less than about 200,000.
 12. Themethod of claim 11 wherein said starch-based polysaccharide is derivedfrom potato or tapioca.
 13. The method of claim 12 wherein saidhydrophobic reagent is an alkenyl succinic anhydride.
 14. The method ofclaim 1, wherein the micellar thickener is non-ionic.
 15. The method ofclaim 1, wherein the micellar thickener is a corona thickener. 16.method of claim 15 wherein the corona thickener has from about 3 toabout 1000 hydrophilic repeat units.
 17. The method of claim 1, whereinthe micellar thickener is linear.
 18. The method of claim 17, whereinthe corona thickener is characterized by the following structure:

in which HRU is a hydrophobic repeat unit, R₁ and R₂ are hydrophobicmoieties, L and L′ are moieties selected from the group consisting ofesters, thioesters, dithioesters, carbonates, thiocarbonates,trithiocarbonates, ethers, thioethers, amides, thioamides,carbamates/urethanes and xanthates, and h is from 3-1000.
 19. The methodof claim 18, wherein the corona thickener is a fatty acid diester of apolyethylene glycol or a fatty acid diester of an ethoxylated fattyalcohol.
 20. The method of claim 1, wherein the healthcare compositionhas a foam generation rate of at least about 10 mL/cycle.
 21. The methodof claim 1, wherein the micellar thickener is present in an amountsufficient to increase the viscosity of the composition at least about100 cP.
 22. The method of claim 1, wherein the micellar thickener has abranched or star-shaped configuration.
 23. The method of claim 15,wherein the corona thickener is a fatty acid polyester of an ethoxylatedglucoside.
 24. The method of claim 1, wherein the superhydrophilicamphiphilic copolymer comprises a plurality of SRUs and at least one ARUthat are derived from one or more monosaccharides selected from thegroup consisting of fructose, glucose, galactose, mannose, guluronicacid, galacturonic acid, fructosamine, glucosamine, and combinationsthereof, and wherein the micellar thickener has from about 3 to about1000 hydrophilic repeat units and includes at least two independenthydrophobic moieties, wherein each of the at least two independenthydrophobic moieties have 10 or more carbon atoms.
 25. The method ofclaim 1, wherein the micellar thickener is a core thickener.
 26. Themethod of claim 1, wherein the micellar thickener is glycerol-based. 27.The method of claim 1 wherein said composition is in the form of ashampoo, wash, bath additive, gel, lotion, or cream.
 28. The method ofclaim 1 wherein said composition further comprises an active fortreating skin condition selected from the group consisting of acne,wrinkles, dermatitis, dryness, muscle pain, itch, or combinations of twoor more thereof.
 29. The method of claim 1 wherein said composition isapplied to human skin, hair, or vaginal region.